CN111073153B - Low-temperature high-toughness impact-resistant polypropylene composition and preparation method thereof - Google Patents
Low-temperature high-toughness impact-resistant polypropylene composition and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of polypropylene materials, and discloses a low-temperature high-toughness impact-resistant polypropylene composition and a preparation method thereof, wherein the low-temperature high-toughness impact-resistant polypropylene composition contains impact-resistant polypropylene, a nucleating agent, petroleum resin and a processing aid, wherein the nucleating agent contains a beta compound nucleating agent, the content of the beta compound nucleating agent is 0.05-0.6 part by weight, the content of the petroleum resin is 1-10 parts by weight and the content of the processing aid is 0.05-4 parts by weight based on 100 parts by weight of the impact-resistant polypropylene; the beta compound nucleating agent is a compound composition of nano powder rubber and the beta nucleating agent. The impact strength of the polypropylene composition can be improved by more than 30% under the zero-temperature condition, the impact performance can be improved by more than 600% under the temperature of minus 20 ℃, the original modulus level is maintained, and the shrinkage rate is reduced.
Description
Technical Field
The invention belongs to the field of polypropylene materials, and particularly relates to a low-temperature high-toughness impact-resistant polypropylene composition and a preparation method thereof.
Background
Impact polypropylene specialties are heterophasic copolymers produced by incorporating a rubberized ethylene-propylene copolymer in a semi-crystalline propylene homopolymer matrix. The impact-resistant polypropylene product is applied to various industries, such as production of small household appliance parts, turnover boxes, bottles, refrigerator drawers, automobile parts, washing machine impellers, paint buckets, air conditioner shells, large containers, heavy-load packages and the like, can also be used for production of pipes, plates, battery shells and the like, and can also be used as a base material of other high-performance polypropylene special material products. The Ethylene Propylene Rubber (EPR) content in the high impact polypropylene (HIPP) is low, and the impact strength is low; increasing the EPR content tends to result in a large loss in rigidity, heat resistance, and the like of the material. It is significant to further increase the impact strength of the HIPP without losing the rigidity and heat resistance of the material, or to increase the rigidity or heat distortion temperature of the HIPP while maintaining its good impact strength.
Feng Jiachun research the effect of rare earth beta nucleating agent on the performance of high impact polypropylene, and the impact strength, elongation at break and thermal deformation temperature of HIPP can be greatly improved by adding WBG, the normal temperature impact strength of HIPP is improved from 45.3kJ/m to 65.4kJ/m, the improvement range can reach 44.4%, and the low temperature impact strength can also be improved by 28%.
Zhang Chunhuai discloses an impact-resistant weather-resistant polypropylene and a preparation method thereof, wherein the impact-resistant weather-resistant polypropylene comprises polypropylene, polyethylene, a filler, an antioxidant, a light stabilizer, a coupling agent and the like, and mainly keeps the mechanical property of a sample under an illumination condition.
Patent document CN102827450B discloses a method for synthesizing a resin special for a high-ethylene-content polypropylene injection molding barrel, which is to synthesize the resin by a Spheripol ring pipe polypropylene device, add a homopolymer, ethylene, propylene and hydrogen into a gas phase reactor for gas phase copolymerization to obtain copolymer powder with high ethylene-propylene rubber phase content, mix the copolymer powder with an antioxidant, a neutralizer and a nucleating agent according to a formula ratio, improve the product modulus by adding the nucleating agent, and ensure that the melt flow rate of special material granules is 3-5 g/10min.
Patent document CN102558678A discloses a high-transparency and high-modulus impact-resistant modified polypropylene material and a preparation method thereof, wherein the main components comprise homopolymerized polypropylene (the melt flow rate is 5-30 g/10 min), nano calcium carbonate, a sorbitol nucleating agent and the like.
Currently, polypropylene products having both rigidity and impact properties are relatively rare.
Disclosure of Invention
In view of the above situation, the present invention provides a low-temperature high-toughness impact polypropylene composition and a preparation method thereof. By using impact polypropylene in combination with a nucleating agent, petroleum resin, etc., a low-temperature, high-toughness polypropylene composition is obtained, which, when molded into a product, has reduced anisotropy and low shrinkage.
The invention provides a low-temperature high-toughness impact-resistant polypropylene composition, which contains impact-resistant polypropylene, a nucleating agent, petroleum resin and a processing aid, wherein the nucleating agent contains a beta compound nucleating agent, the content of the beta compound nucleating agent is 0.05-0.6 part by weight, the content of the petroleum resin is 1-10 parts by weight and the content of the processing aid is 0.05-4 parts by weight based on 100 parts by weight of the impact-resistant polypropylene; the beta compound nucleating agent is a compound composition of nano powder rubber and the beta nucleating agent.
The second aspect of the invention provides a preparation method of the low-temperature high-toughness impact polypropylene composition, which comprises the steps of adding the components contained in the low-temperature high-toughness impact polypropylene composition into a high-speed stirrer according to the content of the components, mixing, adding the mixed materials into a double-screw extruder, drawing yarns through an oral die, cooling through a water tank, and granulating to obtain the low-temperature high-toughness impact polypropylene composition.
The impact-resistant polypropylene, the beta compound nucleating agent, the petroleum resin and the like are combined, so that the impact strength of the prepared polypropylene composition can be improved by more than 30% under the zero-temperature condition, the impact performance can be improved by more than 600% under the-20 ℃, the original modulus level and the shrinkage rate are maintained, the application of the impact-resistant polypropylene material in automotive plastics, building materials and civil appliances is greatly expanded, and the excellent impact resistance and rigidity level are still maintained even in severe cold extreme climate.
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, the present invention provides a low-temperature high-toughness impact polypropylene composition, which contains impact polypropylene, a nucleating agent, petroleum resin and a processing aid, wherein the nucleating agent contains a beta compound nucleating agent, wherein the content of the beta compound nucleating agent is 0.05 to 0.6 parts by weight, the content of the petroleum resin is 1 to 10 parts by weight, and the content of the processing aid is 0.05 to 4 parts by weight, based on 100 parts by weight of the impact polypropylene; the beta compound nucleating agent is a compound composition of nano powder rubber and the beta nucleating agent.
Preferably, based on 100 parts by weight of the impact-resistant polypropylene, the content of the beta compound nucleating agent is 0.15-0.3 part by weight, the content of the petroleum resin is 1-5 parts by weight, and the content of the processing aid is 0.1-1 part by weight.
In the invention, the weight ratio of the nano-powder rubber to the beta nucleating agent is 1-5: 1, preferably 2-4: 1.
The beta compound nucleating agent is combined with the nucleating agent HPN-20E and/or HPN-600ei for use, so that the polypropylene composition can obtain better low-temperature impact property.
Preferably, the nucleating agent also contains HPN-20E and/or HPN-600ei, and the content of the HPN-20E and/or HPN-600ei is 0.01-0.2 part by weight, preferably 0.02-0.1 part by weight, based on 100 parts by weight of the content of the impact polypropylene. The nucleating agent of the type is beneficial to improving the production efficiency, improving the dimensional stability and simultaneously improving the rigidity and the toughness of the material.
Preferably, the melt index of the impact polypropylene at 230 ℃ under a load of 2.16kg is 0.1-1 g/10min, the weight average molecular weight is 500000-800000, the width of the molecular weight distribution is 5-10, and the rubber phase content is 10-30 wt%.
In the invention, the beta nucleating agent can be a substituted aromatic amide compound, a compound with a condensed ring structure, a compound of a group 1IA metal element salt and dicarboxylic acid, or a compound of lanthanum stearate and stearic acid, and the meaning and range of the beta nucleating agent are known to those skilled in the art. Preferably, the beta nucleating agent is DCHT and/or TMB-5.
Preferably, the nano-powder rubber is one or more of fully vulcanized styrene-butadiene rubber, fully vulcanized carboxylated styrene-butadiene rubber, fully vulcanized nitrile-butadiene rubber, fully vulcanized carboxylated nitrile-butadiene rubber, fully vulcanized acrylate rubber, fully vulcanized ethylene-vinyl acetate rubber, fully vulcanized silicone rubber and fully vulcanized butadiene-styrene-pyridine rubber which are subjected to radiation crosslinking.
In the invention, the beta compound nucleating agent can be obtained commercially or by self-preparation. Firstly, fully vulcanized powdered rubber can be prepared according to the method disclosed in the embodiment of CN1152082C, and then the fully vulcanized powdered rubber and the beta nucleating agent are uniformly mixed according to the proportion to prepare the beta compound nucleating agent.
According to a preferred embodiment of the invention, the beta compound nucleating agent is commercially available VP101T, the melting point is more than or equal to 320 ℃, and the beta compound nucleating agent is compounded with the ultrafine fully-vulcanized powdered styrene butadiene rubber.
In the invention, the petroleum resin is mainly used as a fluidity regulator 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 of a C5-C9 fraction which is a byproduct in petroleum cracking, and is not a high polymer but an oligomer. 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 a C5-C9 petroleum resin, which is an oligomer having a 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 10 parts by weight, preferably 1 to 5 parts by weight.
In the invention, the processing aid can be added according to specific application requirements, and the type and the adding amount of the processing aid are conventional in the field.
Preferably, the processing aid is a lubricant and/or an antioxidant, the lubricant is 0.05 to 0.5 part by weight, preferably 0.1 to 0.2 part by weight, and the antioxidant is 0.1 to 3 parts by weight, preferably 0.2 to 0.8 part by weight, based on 100 parts by weight of the polypropylene.
In the present invention, the lubricant may be selected from lubricants conventionally used in polypropylene materials, and is preferably one or more of calcium stearate, zinc stearate, oleamide, erucamide, and ethylene bis stearamide.
According to the invention, 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. The antioxidant is preferably an antioxidant 1098 and an antioxidant 168, and the mass ratio of the antioxidant 1098 to the antioxidant 168 is 1: 0.8-1.2, and is more preferably 1: 1.
According to a second aspect of the invention, the invention provides a preparation method of the low-temperature high-toughness impact polypropylene composition, the components contained in the low-temperature high-toughness impact 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 wire drawing through an oral die, the mixed materials are cooled by a water tank and granulated, so that the low-temperature high-toughness impact polypropylene composition is obtained.
In the invention, the melting temperature of the mixed materials in the double-screw extruder is 100-210 ℃, and the other parameters which are not limited belong to the conventional technical means in the field.
The polypropylene composition of the invention can improve the impact strength by 34% under the zero-temperature condition, improve the impact performance by 615% under the-20 ℃ condition, maintain the original modulus level, reduce the shrinkage rate and maintain the excellent impact performance and rigidity level even in severe cold extreme climate.
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:
impact-resistant polypropylene, PP8332, produced by Beijing chemical research institute;
VP101T, produced by Beijing chemical research institute;
HPN-20E, manufactured by MILLIKEN corporation, USA;
petroleum resin, OPPERA, EXXON MOBILE;
erucamide, manufactured by Hao Mega chemical Co., ltd., guangzhou city;
antioxidant 1098, antioxidant 168, produced by basf soda 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 impact polypropylene composition sample comprises the following steps: mixing impact-resistant polypropylene, beta compound nucleating agent, nucleating agent HPN-20E, petroleum resin, lubricant and antioxidant in an amount shown in Table 1 in a high-speed stirrer, adding into a double-screw extruder, melting at 100-210 ℃, drawing yarns through an oral die, cooling through a water tank, and granulating.
TABLE 1
After the pellets obtained in examples 1 to 5 and comparative examples 1 to 3 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 10 s), 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 tested 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, after modification, the impact polypropylene has greatly improved low-temperature toughness, and the impact strength of the polypropylene composition prepared from the ingredients in the preferred range can be improved by more than 30% under the zero-temperature condition, the impact performance can be improved by more than 600% under the-20 ℃ condition, the modulus is kept between 0.7 and 0.9GPa, the shrinkage rate is reduced, and the shrinkage anisotropy degree is reduced.
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 (11)
1. The low-temperature high-toughness impact-resistant polypropylene composition is characterized by comprising impact-resistant polypropylene, a nucleating agent, petroleum resin and a processing aid, wherein the nucleating agent comprises a beta compound nucleating agent, the content of the beta compound nucleating agent is 0.05 to 0.6 part by weight, the content of the petroleum resin is 1 to 10 parts by weight and the content of the processing aid is 0.05 to 4 parts by weight based on 100 parts by weight of the impact-resistant polypropylene; the beta compound nucleating agent is VP101T;
the nucleating agent also contains HPN-20E and/or HPN-600ei, and the content of the HPN-20E and/or HPN-600ei is 0.01 to 0.2 part by weight based on 100 parts by weight of the content of the impact-resistant polypropylene.
2. The low-temperature high-toughness impact polypropylene composition according to claim 1, wherein the beta compound nucleating agent is contained in an amount of 0.15 to 0.3 part by weight, the petroleum resin is contained in an amount of 1~5 parts by weight, and the processing aid is contained in an amount of 0.1 to 1 part by weight, based on 100 parts by weight of the impact polypropylene.
3. The low-temperature high-toughness impact polypropylene composition according to claim 1, wherein the content of HPN-20E and/or HPN-600ei is 0.02 to 0.1 parts by weight based on 100 parts by weight of the impact polypropylene.
4. The low-temperature high-toughness impact polypropylene composition according to any one of claims 1 to 3, wherein the impact polypropylene has a melt index of 0.1 to 1g/10min at 230 ℃ under a load of 2.16kg, a weight average molecular weight of 500000 to 800000, a molecular weight distribution width of 5 to 10, and a rubber phase content of 10 to 30wt%.
5. The low-temperature high-toughness impact-resistant polypropylene composition according to any one of claims 1 to 3, wherein the petroleum resin is a C5-C9 petroleum resin.
6. The low temperature, high toughness impact polypropylene composition according to any one of claims 1 to 3, wherein said processing aid is a lubricant and/or an antioxidant; the content of the lubricant is 0.05 to 0.5 weight part and the content of the antioxidant is 0.1 to 3 weight parts based on 100 weight parts of the impact-resistant polypropylene.
7. The low-temperature high-toughness impact polypropylene composition according to claim 6, wherein the lubricant is contained in an amount of 0.1 to 0.2 parts by weight and the antioxidant is contained in an amount of 0.2 to 0.8 parts by weight, based on 100 parts by weight of the impact polypropylene.
8. The low temperature, high toughness and impact polypropylene composition of claim 6, wherein said lubricant is one or more of calcium stearate, zinc stearate, oleamide, erucamide and ethylene bis stearamide.
9. The low temperature high toughness impact polypropylene composition according to claim 6, wherein said 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.
10. The low-temperature high-toughness impact polypropylene composition according to claim 9, wherein the antioxidant is an antioxidant 1098 and an antioxidant 168, and the mass ratio of the antioxidant 1098 to the antioxidant 168 is 1: 0.8 to 1.2.
11. The method for preparing the low-temperature high-toughness impact polypropylene composition as claimed in any one of claims 1 to 10, wherein the components contained in the low-temperature high-toughness impact 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 being subjected to wire drawing through an oral die, the mixture is cooled by a water tank and granulated to obtain the low-temperature high-toughness impact polypropylene composition.
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| CN101429309B (en) * | 2008-10-29 | 2012-04-25 | 上海赛科石油化工有限责任公司 | Impact resistant polypropylene composition and process for producing the same |
| CN103265758B (en) * | 2013-06-03 | 2015-07-29 | 四川大学 | A kind of preparation method of low-temperature flexibility isotatic polypropylene goods |
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