CN111073136A - Low-shrinkage polypropylene composition and preparation method thereof - Google Patents
Low-shrinkage polypropylene composition and preparation method thereof Download PDFInfo
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- CN111073136A CN111073136A CN201811227667.XA CN201811227667A CN111073136A CN 111073136 A CN111073136 A CN 111073136A CN 201811227667 A CN201811227667 A CN 201811227667A CN 111073136 A CN111073136 A CN 111073136A
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- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention belongs to the field of polypropylene materials, and discloses a low-shrinkage polypropylene composition and a preparation method thereof, wherein the low-shrinkage polypropylene composition comprises polypropylene, a nucleating agent, petroleum resin, an inorganic compound filler and a processing aid, wherein the nucleating agent is 0.05-0.5 part by weight, the petroleum resin is 1-20 parts by weight, the inorganic compound filler is 1-60 parts by weight and the processing aid is 0.1-3 parts by weight based on 100 parts by weight of the polypropylene. The polypropylene composition of the invention greatly reduces the shrinkage rate of polypropylene, simultaneously improves the impact property by nearly 1 time, increases the flexural modulus by 33 percent, and reduces the anisotropy degree of shrinkage.
Description
Technical Field
The invention belongs to the field of polypropylene materials, and particularly relates to a low-shrinkage polypropylene composition and a preparation method thereof.
Background
Modified polypropylene is one of the most widely used modified plastics in our daily life. The main application fields of the method are relatively representative of automobile parts and household appliance manufacturing: the automobile comprises an automobile bumper, an instrument panel, a steering wheel, a storage battery shell, a bracket, a mudguard, a crank, a stopper, fan blades, an air conditioner cover and the like; the household appliances comprise an outdoor air-conditioning casing, a washing machine roller, a refrigerator drawer, an electric cooker, an electric heating cup and the like.
Shrinkage control of PP polypropylene modified material is an important aspect of polypropylene modification. The good shrinkage control has important significance for the popularization and the application of the polypropylene modified material, and is an important aspect for ensuring the product quality. Especially, the shrinkage rate is very important when the modified polypropylene is used for replacing the traditional engineering plastics. The commonly used means for reducing the shrinkage of polypropylene are the addition of inorganic fillers, minerals, rubbers, or blending with other polymers, etc. The key point for controlling the molding shrinkage of the polypropylene modified material is to change the crystallinity of the polypropylene.
Patent document CN105131420A discloses an isotropic low-shrinkage polypropylene resin and a preparation method thereof, wherein the resin is obtained by mixing and granulating a polypropylene resin added with a nucleating agent, a lubricant, an acid acceptor and the like. The nucleating agent used is (IR, 2S) -rel-1, 2-cyclohexanedicarboxylic acid calcium salt. The shrinkage rate of the polypropylene resin in the parallel direction is less than 0.7 percent, and the shrinkage rate in the vertical direction is less than 1.2 percent. In the invention, the shrinkage rate difference of the polypropylene in two directions is still large.
Patent document CN102952342A discloses a low shrinkage polypropylene composition and a preparation method thereof, which is composed of polypropylene resin, inorganic powder (talc powder, calcium carbonate, mica or kaolin), metallocene linear low density polyethylene, a toughening agent and a weather-resistant auxiliary agent.
Disclosure of Invention
The invention aims to provide a low-shrinkage polypropylene composition and a preparation method thereof. By using a specific nucleating agent, a petroleum resin, polypropylene and the like in combination, a low-shrinkage polypropylene composition is obtained, and when the composition is molded into a product, both impact properties and flexural modulus are improved, and the shrinkage rate is low.
The invention provides a low-shrinkage polypropylene composition, which comprises polypropylene, a nucleating agent, petroleum resin, an inorganic compound filler and a processing aid, wherein the nucleating agent is 0.05-0.5 part by weight, the petroleum resin is 1-20 parts by weight, the inorganic compound filler is 1-60 parts by weight and the processing aid is 0.1-3 parts by weight based on 100 parts by weight of the polypropylene.
According to the second aspect of the invention, the preparation method of the low-shrinkage polypropylene composition is provided, wherein the components contained in the low-shrinkage polypropylene composition are added into a high-speed stirrer according to the content of the components to be mixed, the mixed materials are added into a double-screw extruder, and after the mixed materials are subjected to drawing through an oral die, the mixed materials are cooled by a water tank and granulated to obtain the low-shrinkage polypropylene composition.
According to the invention, by combining polypropylene, a nucleating agent, petroleum resin, an inorganic compound filler and the like, the prepared polypropylene composition has the advantages of low shrinkage, good isotropic shrinkage, high rigidity and impact property, and contribution to the dimensional stability of a final product, and finds a new application field for the traditional polypropylene material.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a low shrinkage polypropylene composition comprising polypropylene, a nucleating agent, a petroleum resin, an inorganic compound filler and a processing aid, wherein the nucleating agent is contained in an amount of 0.05 to 0.5 parts by weight, the petroleum resin is contained in an amount of 1 to 20 parts by weight, the inorganic compound filler is contained in an amount of 1 to 60 parts by weight, and the processing aid is contained in an amount of 0.1 to 3 parts by weight, based on 100 parts by weight of the polypropylene.
Preferably, the nucleating agent is 0.05 to 0.2 part by weight, the petroleum resin is 1 to 10 parts by weight, the inorganic compound filler is 1 to 50 parts by weight, and the processing aid is 0.1 to 0.5 part by weight, based on 100 parts by weight of the polypropylene.
In the invention, the polypropylene is copolymerized polypropylene, the melt index of the copolymerized polypropylene is 5-20g/10min at 230 ℃ and under the load of 2.16kg, the ethylene content is 5-15 wt%, and the ethylene content in the rubber phase is 25-40 wt%.
According to the present invention, the addition of a nucleating agent to a low shrinkage polypropylene composition can change the crystalline state of polypropylene, promote the formation of fine-sized spherulites, and reduce the shrinkage of polypropylene in the parallel and perpendicular flow directions, i.e., reduce anisotropy. Preferably, the nucleating agent is selected from HPN-20E and/or HPN-600 ei.
In the invention, the petroleum resin is mainly used as a fluidity auxiliary agent and plays a certain role in rigidity increasing. The petroleum resin is a thermoplastic resin produced by the processes of pretreatment, polymerization, distillation and the like, and is not a high polymer but an oligomer, wherein the petroleum resin is a C5-C9 fraction which is a byproduct generated in petroleum cracking. The petroleum resin has good cohesiveness, good intersolubility with rubber and resin, good fluidity, good viscosity, and outstanding initial viscosity, and can improve the wettability of the main material. Preferably, the petroleum resin is C5-C9 petroleum resin which is an oligomer with the molecular weight of 300-3000.
Further, since petroleum resin is a low-melting organic substance, and is easily precipitated when the content is high, and does not function when the content is too low, the content is limited to 1 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 1 to 10 parts by weight.
In the present invention, the inorganic compound filler may be selected from a nanoparticulate inorganic oxide and/or a layered inorganic compound. Preferably, the inorganic compound filler is a nano-particulate inorganic compound and a layered inorganic compound.
According to the present invention, the nano-particulate inorganic compound may be contained in an amount of 10 to 50 parts by weight and the layered inorganic compound may be contained in an amount of 1 to 10 parts by weight, based on 100 parts by weight of the polypropylene. Preferably, the content of the nano-particulate inorganic compound is 20 to 40 parts by weight, and the content of the layered inorganic compound is 1 to 6 parts by weight.
According to the present invention, the nanoparticulate inorganic compound and the layered inorganic compound may be selected from those conventionally used in the art. Preferably, the nanoparticulate inorganic compound is selected from at least one of nano calcium sulfate, nano barium sulfate, and nano silica. Preferably, the layered inorganic compound is selected from at least one of zirconium phosphate, hydrotalcite, and montmorillonite.
In the invention, the processing aid can be added according to the specific application requirements, and the type and the adding amount of the processing aid are selected from the conventional types and the conventional amounts in the field, such as an antioxidant and a lubricant.
According to the invention, the processing aid is preferably an antioxidant, and the antioxidant can be selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant CA, antioxidant 1098, antioxidant 168, antioxidant 626 and antioxidant 636.
Preferably, the antioxidant is antioxidant 1098 and antioxidant 168, and the mass ratio of the antioxidant 1098 to the antioxidant 168 is 1: 0.8-1.2, and more preferably 1: 1.
According to a second aspect of the present invention, the present invention provides a preparation method of the low shrinkage polypropylene composition, wherein the components contained in the low shrinkage polypropylene composition are added into a high speed stirrer according to the content of the components to be mixed, the mixed materials are added into a double screw extruder, and after drawing yarns through an oral die, the raw materials are cooled by a water tank and granulated to obtain the low shrinkage polypropylene composition.
In the invention, the materials are mixed in a high-speed stirrer for 0.5-5 minutes at room temperature, the rotating speed of a motor is set to be 500-.
The polypropylene composition of the invention greatly reduces the shrinkage rate by combining the specific nucleating agent, the petroleum resin, the polypropylene and the like, simultaneously improves the impact property by nearly 1 time, and can increase the flexural modulus by 33 percent.
Specific embodiments of the present invention will be described in more detail below.
The raw materials used in the following examples and comparative examples are as follows:
polypropylene B4908, available from yanshan petrochemical company.
Nucleating agent HPN-600ei, available from Milliken, USA;
petroleum resin, OPPERA, available from EXXON MOBILL, usa;
zirconium phosphate, available from Mianzhu Yaoyonghua chemical Co., Ltd;
nano calcium carbonate, produced by ruicheng xintai nanomaterials ltd;
antioxidant 1098, antioxidant 168, produced by basf bus, germany.
The specific formulations of the examples and comparative examples are shown in table 1, wherein the materials are in parts by weight.
The preparation method of the polypropylene composition sample comprises the following steps: mixing polypropylene, a nucleating agent, petroleum resin, an inorganic compound filler and an antioxidant in an amount shown in Table 1 in a high-speed stirrer, adding the mixture into a double-screw extruder, melting at 210-250 ℃, drawing wires through an oral die, cooling by a water tank, and granulating.
TABLE 1
After the pellets obtained in examples 1 to 5 and comparative examples 1 to 2 were charged into an injection molding machine and injection-molded (the temperature of each stage of the injection molding machine was 180 ℃, 190 ℃, 210 ℃, 210 ℃, 200 ℃, the holding pressure was 50MPa, the holding time was 60s, and the cooling time was 10s), injection-molded samples were prepared and tested, and the specific test results are shown in table 2.
The physical property test of the injection molding sample is carried out according to the national standard respectively: shrinkage was measured according to GB/T17037.4-2003; the impact strength of the gap of the simply supported beam is tested according to GB/T1043-1993; flexural modulus was tested according to GB/T9341-2000.
TABLE 2
As shown in Table 2, the modified polypropylene has greatly reduced shrinkage, improved impact performance by about 1 time, increased flexural modulus by 33%, and reduced anisotropy of shrinkage. In addition, the polypropylene composition produced from the formulation in the preferred range has better performance.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. The low-shrinkage polypropylene composition is characterized by comprising polypropylene, a nucleating agent, petroleum resin, an inorganic compound filler and a processing aid, wherein the nucleating agent is 0.05-0.5 part by weight, the petroleum resin is 1-20 parts by weight, the inorganic compound filler is 1-60 parts by weight and the processing aid is 0.1-3 parts by weight based on 100 parts by weight of the polypropylene.
2. The low shrinkage polypropylene composition according to claim 1, wherein the nucleating agent is contained in an amount of 0.05 to 0.2 parts by weight, the petroleum resin is contained in an amount of 1 to 10 parts by weight, the inorganic compound filler is contained in an amount of 1 to 50 parts by weight, and the processing aid is contained in an amount of 0.1 to 0.5 parts by weight, based on 100 parts by weight of the polypropylene.
3. The low profile polypropylene composition according to claim 1, wherein the polypropylene is a co-polypropylene having a melt index of 5-20g/10min at 230 ℃ under a load of 2.16kg, an ethylene content of 5-15 wt%, and an ethylene content in the rubber phase of 25-40 wt%.
4. The low profile polypropylene composition according to claim 1, wherein the nucleating agent is selected from HPN-20E and/or HPN-600 ei.
5. The low shrinkage polypropylene composition according to claim 1, wherein the petroleum resin is a C5-C9 petroleum resin.
6. The low profile polypropylene composition according to claim 1, wherein the inorganic compound filler is selected from nanoparticulate inorganic compounds and/or layered inorganic compounds.
7. The low profile polypropylene composition according to claim 6, wherein the inorganic compound filler is a nano-particulate inorganic compound and a layered inorganic compound; the content of the nano-particulate inorganic compound is 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the polypropylene; the content of the lamellar inorganic compound is 1 to 10 parts by weight, preferably 1 to 6 parts by weight.
8. The low profile polypropylene composition according to claim 6 or 7, wherein the nanoparticulate inorganic compound is selected from at least one of nano calcium sulfate, nano barium sulfate and nano silica; the layered inorganic compound is at least one selected from the group consisting of zirconium phosphate, hydrotalcite, and montmorillonite.
9. The low-shrinkage polypropylene composition according to claim 1, wherein the processing aid is an antioxidant, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant CA, antioxidant 1098, antioxidant 168, antioxidant 626 and antioxidant 636, preferably the antioxidant 1098 and the antioxidant 168, and the mass ratio of the antioxidant 1098 to the antioxidant 168 is 1: 0.8-1.2.
10. The method for preparing the low-shrinkage polypropylene composition as claimed in any one of claims 1 to 9, wherein the components contained in the low-shrinkage polypropylene composition are added into a high-speed stirrer according to the content of the components, mixed materials are added into a double-screw extruder, and after being subjected to drawing through an oral die, the materials are cooled by a water tank and granulated to obtain the low-shrinkage polypropylene composition.
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| CN201811227667.XA CN111073136A (en) | 2018-10-19 | 2018-10-19 | Low-shrinkage polypropylene composition and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280167A (en) * | 2020-09-28 | 2021-01-29 | 中国石油化工股份有限公司 | Preparation method of heat-resistant high-rigidity transparent low-shrinkage homo-polypropylene resin with wide molecular weight distribution |
| CN114989526A (en) * | 2022-04-08 | 2022-09-02 | 中国石油化工股份有限公司 | Polypropylene composite material and preparation method and application thereof |
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| JP2006082383A (en) * | 2004-09-16 | 2006-03-30 | Mitsubishi Plastics Ind Ltd | Heat-shrinkabie olefin film |
| CN101161736A (en) * | 2007-09-29 | 2008-04-16 | 中国蓝星（集团）总公司 | Special coating resin combination for polypropylene heavy-load packaging bag and preparation method thereof |
| CN102952342A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Low-shrinkage polypropylene composition and preparation method thereof |
| CN107686598A (en) * | 2017-09-15 | 2018-02-13 | 深圳市欧龙优新材料科技有限公司 | A kind of low-shrinkage low-gravity modified polypropylene material and preparation method thereof |
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2018
- 2018-10-19 CN CN201811227667.XA patent/CN111073136A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006082383A (en) * | 2004-09-16 | 2006-03-30 | Mitsubishi Plastics Ind Ltd | Heat-shrinkabie olefin film |
| CN101161736A (en) * | 2007-09-29 | 2008-04-16 | 中国蓝星（集团）总公司 | Special coating resin combination for polypropylene heavy-load packaging bag and preparation method thereof |
| CN102952342A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Low-shrinkage polypropylene composition and preparation method thereof |
| CN107686598A (en) * | 2017-09-15 | 2018-02-13 | 深圳市欧龙优新材料科技有限公司 | A kind of low-shrinkage low-gravity modified polypropylene material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280167A (en) * | 2020-09-28 | 2021-01-29 | 中国石油化工股份有限公司 | Preparation method of heat-resistant high-rigidity transparent low-shrinkage homo-polypropylene resin with wide molecular weight distribution |
| CN114989526A (en) * | 2022-04-08 | 2022-09-02 | 中国石油化工股份有限公司 | Polypropylene composite material and preparation method and application thereof |
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Application publication date: 20200428 |