CN115710381A - Polypropylene composite additive and application thereof - Google Patents
Polypropylene composite additive and application thereof Download PDFInfo
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- CN115710381A CN115710381A CN202211355510.1A CN202211355510A CN115710381A CN 115710381 A CN115710381 A CN 115710381A CN 202211355510 A CN202211355510 A CN 202211355510A CN 115710381 A CN115710381 A CN 115710381A
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Abstract
The invention relates to the field of plastic additives, in particular to a high-melt-index high-impact polypropylene composite additive and application thereof, wherein the composite additive comprises a nucleating agent and a nucleating agent carrier, wherein the nucleating agent comprises a first nucleating agent and a second nucleating agent, and the first nucleating agent is 2,2 '-methylene-bis (4,6-di-tert-butyl benzene) sodium phosphate or bis [2,2' -methylene-bis (4,6-di-tert-butyl phenyl) ] aluminium phosphate; the second nucleating agent is one or more of tert-butyl aluminum hydroxy benzoate, sodium benzoate, calcium hexahydrophthalate and hydrated magnesium silicate, and the nucleating agent carrier is nano hydrotalcite. The nano hydrotalcite is used as a carrier, and a plurality of nucleating agent combinations are added, so that the flexural modulus and the impact strength of the polypropylene copolymer are greatly improved, the rigidity and toughness balance of a polypropylene product is realized, and the performance requirements of the high melt index, high modulus and high impact resistance polypropylene are met.
Description
Technical Field
The invention relates to the field of plastic additives, in particular to a high-melt-index high-modulus high-impact-resistance polypropylene composite additive and application thereof.
Background
The invention belongs to the technical field of plastic additives and application in high polymers, and particularly relates to preparation of a polypropylene-containing composite additive and application thereof in high melt index high modulus high impact polypropylene;
polypropylene is a thermoplastic resin commonly used at present, homopolymerized polypropylene (PP-H) is polymerized by a single propylene monomer, and a molecular chain does not contain an ethylene monomer, so that the regularity of the molecular chain is high, and the crystallinity of the material is high, but the impact resistance is poor. In order to improve the brittleness problem of PP-H, part of raw material suppliers also adopt a method of blending and modifying polyethylene and ethylene propylene rubber to improve the toughness of the material, but cannot essentially solve the long-term heat-resistant stability of PP-H. In order to solve the defects of poor impact resistance (brittleness), poor toughness, poor dimensional stability, easy aging and poor long-term heat-resistant stability of the homo-polypropylene (PP-H), the industry technicians propose the co-polypropylene to improve the technical defects. Copolymerization modification is a typical modification way, and propylene monomers are mainly copolymerized and polymerized with other olefin monomers in a polymerization stage to improve the low-temperature toughness, impact resistance, transparency and processing flowability of polypropylene. The polypropylene copolymer can be divided into two types, namely random (random) polypropylene copolymer (PP-R) and block (impact-resistant) polypropylene copolymer (PP-B), wherein the random (random) polypropylene copolymer (PP-R) is obtained by copolymerizing a propylene monomer and a small amount of ethylene (1-4%) monomer under the action of heat, pressure and a catalyst, and the ethylene monomer is randomly and randomly distributed in the long chain of the propylene. The random addition of ethylene reduces the crystallinity and melting point of the polymer, and improves the properties of the material in the aspects of impact, long-term hydrostatic pressure resistance, long-term thermal-oxidative aging resistance, pipe processing and forming and the like. Indexes such as PP-R molecular chain structure, ethylene monomer content and the like have direct influence on long-term thermal stability, mechanical property and processability of the material. The more random the distribution of ethylene monomers in the propylene molecular chain, the more marked the change in polypropylene properties. The random (random) copolymer polypropylene (PP-R) has the advantages of good comprehensive performance, high strength, large rigidity, good heat resistance, good dimensional stability, excellent low-temperature toughness (good flexibility), good transparency and good glossiness. However, the impact resistance of the polypropylene is insufficient, and in order to improve the impact resistance, the block (impact resistant) polypropylene copolymer (PP-B) appears, the ethylene content of the polypropylene is higher and is generally 7-15%, but because the probability that two ethylene monomers and three monomers in the PP-B are connected together is very high, the ethylene monomers only exist in a block phase, and the regularity of PP-H is not reduced, so that the performance aims of improving the melting point of PP-H, long-term hydrostatic pressure resistance, long-term thermal-oxidative aging resistance, pipe processing forming and the like are not achieved. Although the block (impact) copolymer polypropylene (PP-B) can improve impact resistance, it has a problem in that transparency and gloss are reduced.
Based on the above properties of the copolymerized polypropylene, it is known that the impact of the ethylene content of the ethylene-propylene copolymer on the flexural modulus and impact resistance of the copolymer is opposite, i.e., increasing the copolymerization amount of ethylene can increase the impact resistance of the copolymer, but the flexural modulus is significantly reduced, and when high modulus is required, the copolymerization amount of ethylene needs to be reduced, and then the impact resistance is reduced. In actual needs, polymers with a certain high modulus and impact resistance are often needed, for example, when manufacturing some large thin-walled products, such as large parts in the fields of automobiles, household appliances and the like. Those skilled in the art have continuously optimized the "three high two low" (high melt index, high modulus, high impact resistance, low odor, low VOC) properties of co-polypropylene for these large thin-walled articles. It is desired by those skilled in the art to formulate a high melt, high modulus, high impact polypropylene having excellent mechanical properties, chemical stability, and creep resistance.
At present, according to market demands, the melt index is more than 30g/10min, and the impact strength is more than 5kj per square meter; the modified polypropylene copolymer with the flexural modulus of more than 1500MPa can meet the high melt index high modulus high impact resistant polypropylene required by the automobile industry, and the invention hopes to simultaneously improve the flexural modulus and the impact resistant performance of the polypropylene, improve the transparency and the glossiness thereof and realize good rigidity-toughness balance thereof by compounding the auxiliary agent so as to meet the high performance requirements of different industries on the high melt index high modulus high impact resistant polypropylene.
Disclosure of Invention
In order to improve the flexural modulus and the impact resistance of the polypropylene copolymer and realize the performance requirement of rigidity-toughness balance, the invention provides a composite additive for preparing high-melt-index high-modulus high-impact polypropylene, which is applied to the three-high modification of block polypropylene copolymer with the ethylene content of 3-10 wt% and the isotacticity of more than 96%.
The invention provides a polypropylene composite additive, which comprises a nucleating agent and a nucleating agent carrier, and is characterized in that the nucleating agent comprises a first nucleating agent and a second nucleating agent, wherein the first nucleating agent is 2,2 '-methylene-bis (4,6-di-tert-butylphenyl) sodium phosphate or bis [2,2' -methylene-bis (4,6-di-tert-butylphenyl) ] aluminum phosphate; the second nucleating agent is one or more of tert-butyl aluminum hydroxy benzoate, sodium benzoate, calcium hexahydrophthalate and hydrated magnesium silicate, and the nucleating agent carrier is nano hydrotalcite.
Preferably, mgO/Al of the nano hydrotalcite 2 O 3 The mol ratio is 4.0 to 4.5, and the specific surface area is more than or equal to 15m 2 (iv) g, the average particle diameter is 1.0 μm or less.
Preferably, the grain diameter of the second nucleating agent is D50 less than or equal to 5 μm; d100 is less than or equal to 30 mu m.
Preferably, the weight ratio of the first nucleating agent to the second nucleating agent is 1 (0.1-10), preferably 1:1.
Preferably, the antioxidant comprises a main antioxidant, and the main antioxidant is one or a mixture of more than one of antioxidant 1010, antioxidant 3114, antioxidant 330, antioxidant 1790 and antioxidant 1076.
Further, the antioxidant comprises an auxiliary antioxidant, and the auxiliary antioxidant is one or a mixture of more than one of antioxidant 168, antioxidant 626, antioxidant DBHA and antioxidant DBHB.
Preferably, the acid-absorbing agent is one or more of sodium myristate, sodium laurate, sodium stearate, potassium myristate, potassium laurate, potassium stearate, zinc myristate, zinc stearate, calcium myristate, calcium stearate, calcium laurate, zinc laurate, and hydrotalcite.
The second purpose of the invention is to provide a specific application of the polypropylene composite additive, which is used for modifying the copolymerized polypropylene, wherein the ethylene content of the copolymerized polypropylene is 3-10 wt%, preferably 5-7 wt%, and the melt index is more than 30g/10min.
Preferably, the polypropylene copolymer is block homo-polypropylene with isotacticity of more than 96%.
Preferably, the modified polypropylene copolymer has a flexural modulus of more than 1600MPa and an impact strength of more than 5.5.
Compared with the prior art, the polypropylene composite additive provided by the invention has the following beneficial effects:
firstly, a plurality of nucleating agents are creatively added in a combined manner, so that the flexural modulus of polypropylene is greatly improved, the impact strength of the polypropylene is improved to a certain extent, the rigidity and toughness balance of polypropylene products is realized, and the performance requirement of high-melt-index high-modulus high-impact polypropylene is met.
Secondly, functional components of the composite auxiliary agent are combined, so that the polypropylene is not influenced by other inorganic fillers and pigments in the modification process.
Thirdly, through the modification of the composite auxiliary agent, the lightweight is realized under the condition of ensuring the mechanical property requirement of the material, so that the use requirement of the lightweight automobile modified material is met.
Detailed Description
The polypropylene compounding aid provided by the present invention is further described below with reference to specific embodiments, and it should be noted that the technical solution and design principle of the present invention are described in detail below only with the optimized technical solution.
The polypropylene composite additive comprises a nucleating agent and a nucleating agent carrier, and is characterized in that the nucleating agent comprises a first nucleating agent and a second nucleating agent, wherein the first nucleating agent is 2,2 '-methylene-bis (4,6-di-tert-butylphenyl) sodium phosphate or bis [2,2' -methylene-bis (4,6-di-tert-butylphenyl) ] aluminium phosphate; the second nucleating agent is one or more of tert-butyl aluminum hydroxy benzoate, sodium benzoate, calcium hexahydrophthalate and hydrated magnesium silicate, and the nucleating agent carrier is nano hydrotalcite.
Wherein, the MgO/Al of the nano hydrotalcite 2 O 3 The mol ratio is 4.0 to 4.5, and the specific surface area is more than or equal to 15m 2 The average grain diameter is less than or equal to 1.0 mu m, the first nucleating agent is a product sold on the market at present, and the grain diameter of the second nucleating agent meets the requirement that D50 is less than or equal to 5 mu m; when the D100 is less than or equal to 30 mu m, the modification effect is better.
According to experimental detection, when the weight ratio of the first nucleating agent to the second nucleating agent is 1 (0.1-10), the three-high modification effect on polypropylene is remarkable, and particularly the three-high modification effect on the polypropylene copolymer is most remarkable when the weight ratio of the first nucleating agent to the second nucleating agent is 1:1.
The preparation process of the polypropylene composite additive comprises the steps of firstly, fully mixing a first nucleating agent and a second nucleating agent according to a ratio to form a nucleating agent component, then adding the nucleating agent component into nano hydrotalcite serving as a nucleating agent carrier, and fully stirring to enable the nucleating agent component to be uniformly loaded on the nano hydrotalcite carrier to form a main component of the polypropylene composite additive.
The antioxidant matched with the main component of the polypropylene composite auxiliary agent comprises a main antioxidant, wherein the main antioxidant is one or a mixture of more than one of antioxidant 1010, antioxidant 3114, antioxidant 330, antioxidant 1790 and antioxidant 1076. The antioxidant can also comprise an auxiliary antioxidant, and the auxiliary antioxidant is one or a mixture of more than one of antioxidant 168, antioxidant 626, antioxidant DBHA and antioxidant DBHB.
The acid absorbing agent matched with the main component of the polypropylene composite auxiliary agent can be one or more of sodium myristate, sodium laurate, sodium stearate, potassium myristate, potassium laurate, potassium stearate, zinc myristate, zinc stearate, calcium myristate, calcium stearate, calcium laurate and zinc laurate.
The following specific examples further illustrate the composition of the polypropylene composite additive and experimental comparison of the three-high modification effect of the copolymerized polypropylene.
The polypropylene copolymer composite additive is subjected to component blending and modification experiments, typically, a first nucleating agent is 2,2' -methylene-bis (4,6-di-tert-butylbenzene) sodium phosphate, a second nucleating agent is subjected to experiments by using calcium hexahydrophthalate, and the components of the specific composite additive are prepared according to the mass parts shown in table 1:
| component (parts by mass) | A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | A9 |
| A first nucleating agent | 9 | 7 | 5 | 1.7 | 0.9 | 0.6 | 10 | ||
| Second nucleating agent | 1 | 3 | 5 | 8.3 | 9.1 | 9.4 | 10 | ||
| Nano hydrotalcite | 3 | 3 | 3 | 3 | 3 | 3 | |||
| Calcium stearate | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Antioxidant 1010 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Antioxidant 168 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
Table 1 shows the components of the compound assistant experiment
The polypropylene composite additive samples A1 to A9 obtained in table 1 were used for modification tests of copolymerized polypropylene having ethylene contents of 5%, 7% and 10% in an amount of 0.3 part by mass, respectively, and the experimental numbers are shown in table 2.
Table 2: experimental number of modified polypropylene copolymer of polypropylene composite additive
The samples shown in Table 2 were evaluated according to the test standards ISO527, ISO11357, GB/T9341-2008, GB/T1843, GB/T1634 and ISO1133, respectively, for tensile yield strength, crystallization temperature, flexural modulus, impact strength and heat distortion temperature, and the test results of the modified test samples are shown in Table 3.
Table 3 shows the results of modification tests of the test samples in Table 2
Through the detection results in table 3, it can be seen that after the composite additive provided by the present invention is added, the flexural modulus and the impact strength of the copolymerized polypropylene with ethylene content of 5%, 7% and 10% are both significantly improved, and especially, the flexural modulus of the copolymerized polypropylene with ethylene content of 5% and 7% can be improved to more than 1500MPa while the impact strength is maintained at 5.5kJ/m in the composite additives A1 to A5 with the weight ratio of the first nucleating agent to the second nucleating agent being 1 (0.1-10) 2 The above. In particular to a compound additive A3 sample with the weight ratio of the first nucleating agent to the second nucleating agent of 1:1, the flexural modulus and the impact strength of the copolymerized polypropylene with the ethylene content of 5 percent are reduced from the original flexural modulus and the impact strength of 1295MPa,5.3kJ/m 2 Is obviously increased to 1705MPa,5.8kJ/m 2 The bending modulus and impact strength of the copolymerized polypropylene with the ethylene content of 7% are from 1205MPa 2 The temperature is obviously increased to 1635MPa,6.3kJ/m 2 The modified polypropylene has excellent rigidity-toughness balance for the modification of polypropylene copolymer products.
In addition, the inventor also carries out an influence experiment on the addition of the inorganic filler and the pigment to the composite additive, and the experiment proves that the addition of the inorganic filler and the pigment does not cause obvious reduction on the three-high modification effect of the composite additive in the polypropylene copolymer.
The foregoing is merely a preferred embodiment of the invention, and it is noted that the use of the terms "a" and "an" and "the" and similar referents herein is to be construed to cover both the singular and the plural, unless otherwise indicated; the terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms; recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, each separate value being incorporated into the specification as if it were individually recited herein; all methods described herein can be performed in any suitable order. The use of any and all examples, or exemplary language, provided herein is intended merely to better illuminate the subject matter of the application and does not pose a limitation on the scope of the subject matter unless otherwise claimed.
Preferred embodiments of the subject matter of this application, including the best mode known to the inventors for carrying out the claimed subject matter, are described herein, and should not be taken as limiting the invention, which is defined by the scope of the claims. Any variations which may be made by a person skilled in the art in light of the above description of preferred embodiments will be considered obvious by the detailed description herein. Therefore, it will be apparent to those skilled in the art that various modifications, substitutions, improvements and decorations can be made without departing from the spirit and scope of the invention and these modifications, substitutions, improvements and decorations should also be regarded as the protection scope of the invention.
Claims (10)
1. A polypropylene compounding aid comprising a nucleating agent, a nucleating agent carrier, wherein the nucleating agent comprises a first nucleating agent and a second nucleating agent, wherein the first nucleating agent is 2,2 '-methylene-bis (4,6-di-tert-butylphenyl) sodium phosphate or bis [2,2' -methylene-bis (4,6-di-tert-butylphenyl) ] aluminum phosphate; the second nucleating agent is one or more of tert-butyl aluminum hydroxy benzoate, sodium benzoate, calcium hexahydrophthalate and hydrated magnesium silicate, and the nucleating agent carrier is nano hydrotalcite.
2. The polypropylene composite adjuvant of claim 1 wherein the nano-scale water is slipperyMgO/Al of stone 2 O 3 The mol ratio is 4.0 to 4.5, and the specific surface area is more than or equal to 15m 2 (iv)/g, the average particle diameter is 1.0 μm or less.
3. The polypropylene composite additive as claimed in claim 1, wherein the weight ratio of the first nucleating agent to the second nucleating agent is 1 (0.1-10).
4. The polypropylene compounding aid of claim 3, wherein the weight ratio of the first nucleating agent to the second nucleating agent is 1:1.
5. The polypropylene compounding aid of claim 1, wherein the compounding aid further comprises an antioxidant, the antioxidant comprises a primary antioxidant, and the primary antioxidant is one or a mixture of more than one of the group consisting of antioxidant 1010, antioxidant 3114, antioxidant 330, antioxidant 1790, and antioxidant 1076.
6. The polypropylene compounding aid of claim 5, wherein the antioxidant further comprises an auxiliary antioxidant, and the auxiliary antioxidant is one or more of antioxidant 168, antioxidant 626, antioxidant DBHA and antioxidant DBHB.
7. The polypropylene composite additive according to claim 1, further comprising an acid absorbent, wherein the acid absorbent is one or more selected from the group consisting of sodium myristate, sodium laurate, sodium stearate, potassium myristate, potassium laurate, potassium stearate, zinc myristate, zinc stearate, calcium myristate, calcium stearate, calcium laurate, and zinc laurate.
8. The use of a polypropylene composite additive according to any one of claims 1 to 7 for modifying a polypropylene copolymer, wherein the modified polypropylene copolymer has a flexural modulus of greater than 1600MPa and an impact strength of greater than 5.5.
9. Use according to claim 8, wherein the copolypropylene has an ethylene content of 5 to 7 wt.% and a melt index of > 30g/10min.
10. Use according to claim 9, wherein the co-polypropylene is a block co-polypropylene with an isotacticity > 96%.
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| CN104262786A (en) * | 2014-10-17 | 2015-01-07 | 贵州省材料产业技术研究院 | Composite polypropylene nucleating agent as well as preparation method and application thereof |
| CN104530483A (en) * | 2014-10-17 | 2015-04-22 | 贵州省材料产业技术研究院 | Preparation method of hybrid nucleating agent with ultrafine inorganic silica sol as carrier |
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- 2022-11-01 CN CN202211355510.1A patent/CN115710381A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157771A (en) * | 2007-09-29 | 2008-04-09 | 中山大学 | Supported beta crystal core formation agent and preparation method thereof |
| CN101580601A (en) * | 2009-06-12 | 2009-11-18 | 中山大学 | Metal oxide supported beta-crystal nucleating agent and preparation method of beta-crystal nucleating agent |
| CN101845171A (en) * | 2010-04-20 | 2010-09-29 | 广州呈和科技有限公司 | Polypropylene reinforcement nucleating agent composition |
| CN103571123A (en) * | 2012-07-20 | 2014-02-12 | 中国石油化工股份有限公司 | Antishock polypropylene composition used for automobile bumper and preparation method of the composition |
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