CN107325403B - Polypropylene plastic containing composite nucleating agent and preparation method thereof - Google Patents
Polypropylene plastic containing composite nucleating agent and preparation method thereof Download PDFInfo
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- CN107325403B CN107325403B CN201710574771.5A CN201710574771A CN107325403B CN 107325403 B CN107325403 B CN 107325403B CN 201710574771 A CN201710574771 A CN 201710574771A CN 107325403 B CN107325403 B CN 107325403B
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
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Abstract
The invention relates to a polypropylene plastic containing a composite nucleating agent and a preparation method thereof. Compared with the common polypropylene plastic, the polypropylene plastic has obvious advantages in the aspects of impact resistance and the like, and has the advantages of simple preparation, high production efficiency and the like.
Description
Technical Field
The invention relates to a plastic material, in particular to a polypropylene plastic material containing a nucleating agent.
Background
Polypropylene is a thermoplastic resin material with excellent comprehensive performance, has rich raw material sources, is easy to modify, and is widely applied to various fields of production and life. However, polypropylene has some disadvantages such as poor cold resistance, brittleness at low temperature, large shrinkage, poor creep resistance, poor dimensional stability of products, and easy occurrence of warp deformation. The addition of nucleating agents is an effective method for improving the performance of polypropylene.
The polyolefin nucleating agent is a new functional assistant which can accelerate the crystallization rate, increase the crystallization density and promote the grain size to be micronized by changing the crystallization behavior of the resin, thereby achieving the purposes of shortening the molding cycle and improving the physical and mechanical properties of the product, such as transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance and the like.
The polypropylene nucleating agent can be divided into inorganic nucleating agent, organic nucleating agent and high-melting point polymer according to different molecular structures of the nucleating agent. Inorganic nucleating agents begin earlier and less expensive, and nucleate less well than organic nucleating agents. Mainly comprises talcum powder, carbon black, various silica gels and other fillers. The main disadvantages are that it is easy to create two phases with polypropylene, lack of affinity, resulting in reduced PP properties, affecting high transparency and limiting PP applications. The most varied are organic nucleating agents such as carboxylic acids and carboxylates, sorbitol, phosphates and rosins. The carboxylic acid and the carboxylate have poor compatibility with the polymer, the modification effect is not obvious, and the carboxylic acid and the carboxylate are rarely used. High melting polymeric nucleators, which were introduced into polypropylene articles only after the end of the eighties, may have better compatibility with the polymer. So far, few commercial varieties of single high-melting-point polyolefin nucleating agents are on the market, and the main varieties are polyvinylcyclohexane, polyvinylpentane and the like.
Cyclodextrin (CD) is a cyclic oligosaccharide which is formed by connecting a plurality of D-glucopyranoses through alpha-1, 4-glycosidic bonds and has unique cone-cylinder-shaped cavities with inner hydrophobicity and outer hydrophilicity, wherein alpha-CD, beta-CD and gamma-CD are common. The beta-CD polymerized by 7 glucose units has simple production process and lower cost, and the cavity of the beta-CD is more suitable, so the beta-CD is a cyclodextrin product which is widely applied at present. The cyclodextrin and the cyclodextrin derivative have aqueous cavities and can form an inclusion compound with various guest medicaments, so that the solubility and the medicament stability of the medicaments can be improved, the cyclodextrin and the cyclodextrin derivative are medicament carriers with good effects of increasing the solubility and improving the medicament stability of the medicaments at present, but the cyclodextrin and the cyclodextrin derivative are less researched as a nucleating agent of a polypropylene material.
Disclosure of Invention
The invention aims to provide a modified impact-resistant polypropylene plastic material which has obvious advantages in the aspects of impact resistance and the like compared with common polypropylene plastics, has the advantages of simple preparation, high production efficiency and the like, and can quickly solve the defects of poor toughness and ageing resistance of the traditional polypropylene plastics.
The technical scheme of the invention is as follows: the polypropylene plastic comprises isotactic polypropylene and a composite nucleating agent as raw materials, wherein the composite nucleating agent consists of an inclusion compound of cyclodextrin and derivatives thereof and a synergist, and the synergist is phthalic acid calcium glycinate.
Preferably, the inclusion complex of cyclodextrin and its derivatives is selected from beta-cyclodextrin inclusion complex, gamma-cyclodextrin inclusion complex or hydroxypropyl-beta-cyclodextrin inclusion complex; more preferably, it is selected from hydroxypropyl-beta-cyclodextrin inclusion compounds.
Preferably, the inclusion compound of cyclodextrin and its derivative is an inclusion compound of cyclodextrin and its derivative and isotactic polypropylene.
Preferably, the preparation method of the inclusion compound of the cyclodextrin and the derivative thereof comprises the following steps: dissolving isotactic polypropylene in 1,2, 4-trichlorobenzene, stirring at high temperature in nitrogen atmosphere until the solution is clear, dissolving another equimolar cyclodextrin and a derivative thereof in dimethyl sulfoxide, heating the dimethyl sulfoxide solution, slowly dropwise adding the dimethyl sulfoxide solution into the isotactic polypropylene solution, cooling to room temperature after the reaction is finished, filtering reaction liquid to obtain a precipitate, washing the precipitate with hot 1,2, 4-trichlorobenzene solution, water and acetone in sequence, and drying the washed precipitate at room temperature in vacuum to obtain the finished product.
Preferably, the weight ratio of the isotactic polypropylene to the double-nuclear nucleating agent is 100:0.05-0.5, more preferably 100:0.1-0.2, and most preferably 100: 0.2.
Preferably, the weight ratio of the inclusion compound of the cyclodextrin and the derivative thereof to the synergist is 10:1-1: 10; more preferably, the weight ratio is 3:1 to 1: 3.
Preferably, the raw material of the polypropylene plastic further comprises an antioxidant and/or an ultraviolet resistant agent.
The other technical scheme of the invention is as follows: a process for preparing polypropylene plastics includes proportionally mixing isotactic polypropylene, composite nucleating agent, antioxidizing agent and/or uvioresistant agent, stirring, granulating at 185 deg.C, drying, and injection moulding at 200 deg.C.
The technical scheme of the invention has the beneficial effects that:
the inventor surprisingly finds that the inclusion compound formed by the isotactic polypropylene wrapped by cyclodextrin and the derivative thereof can be used as a good nucleating agent of polypropylene, has better nucleating effect when used together with the phthalic acid glycine calcium, and has unexpected excellent effect on improving the impact resistance of the polypropylene.
Detailed Description
Example 1 preparation of isotactic Polypropylene/hydroxypropyl-beta-Cyclodextrin Inclusion Complex
Dissolving 0.02mol of isotactic polypropylene in 800ml of 1,2, 4-trichlorobenzene, stirring at 120 ℃ under the nitrogen atmosphere until the isotactic polypropylene is clear, dissolving 0.02mol of hydroxypropyl-beta-cyclodextrin in 80ml of dimethyl sulfoxide, heating the dimethyl sulfoxide solution to 120 ℃, slowly dripping the solution into the polypropylene solution, and continuously stirring at 120 ℃ for 4 hours after dripping. After the reaction is finished, cooling the reaction liquid to room temperature, continuously stirring for 24 hours, filtering the reaction liquid to obtain a precipitate, washing the precipitate by using hot 1,2, 4-trichlorobenzene solution, water and acetone in sequence, and drying the washed precipitate in vacuum for 24 hours at room temperature to obtain the hydroxypropyl-beta-cyclodextrin inclusion compound wrapping the polypropylene.
Example 2 preparation of modified Polypropylene PP1
Uniformly stirring and mixing 100 parts by weight of isotactic polypropylene and 0.2 part by weight of hydroxypropyl-beta-cyclodextrin inclusion compound prepared in example 1 in a stirrer, extruding at 185 ℃ and granulating; and drying the granules, and performing injection molding at the temperature of 200 ℃ to obtain the modified polypropylene PP 1.
Example 3 preparation of modified Polypropylene PP2
Uniformly stirring and mixing 100 parts by weight of isotactic polypropylene and 0.2 part by weight of calcium phthaloyl glycinate in a stirrer, extruding at 185 ℃ and granulating; and drying the granules, and performing injection molding at the temperature of 200 ℃ to obtain the modified polypropylene PP 2.
Example 4 preparation of modified Polypropylene PP3
Uniformly stirring and mixing 100 parts by weight of isotactic polypropylene, 0.1 part by weight of hydroxypropyl-beta-cyclodextrin inclusion compound prepared in example 1 and 0.1 part by weight of calcium phthaloyl glycinate in a stirrer, extruding at 185 ℃ and granulating; and drying the granules, and performing injection molding at the temperature of 200 ℃ to obtain the modified polypropylene PP 3.
Example 5 preparation of modified Polypropylene PP4
Uniformly stirring and mixing 100 parts by weight of isotactic polypropylene, 0.05 part by weight of hydroxypropyl-beta-cyclodextrin inclusion compound prepared in example 1 and 0.15 part by weight of calcium phthaloyl glycinate in a stirrer, extruding at 185 ℃ and granulating; and drying the granules, and performing injection molding at the temperature of 200 ℃ to obtain the modified polypropylene PP 4.
Example 6 preparation of modified Polypropylene PP5
Uniformly stirring and mixing 100 parts by weight of isotactic polypropylene, 0.15 part by weight of hydroxypropyl-beta-cyclodextrin inclusion compound prepared in example 1 and 0.05 part by weight of calcium phthaloyl glycinate in a stirrer, extruding at 185 ℃ and granulating; and drying the granules, and performing injection molding at the temperature of 200 ℃ to obtain the modified polypropylene PP 5.
Test example 1 mechanical property test and Heat distortion temperature test of Polypropylene containing composite nucleating agent
The modified polypropylene PP1-PP5 materials of examples 2-6 were tested for properties using unmodified, pure isotactic polypropylene as a control. The notched Izod impact strength is tested according to GB/T1843-2008 by using a Izod impact tester XJU-5.5, the thermal deformation temperature is tested according to GB/T1634.2-2004 by using a thermal deformation and Vicat softening point temperature tester XWB-300B, and specific test results are shown in Table 1.
TABLE 1 notched Izod impact Strength and Heat distortion temperature for each test group
From the test results, the inclusion compound of cyclodextrin and the derivative thereof and the addition of the calcium phthaloyl glycinate synergist greatly improve the impact strength of polypropylene and the thermal deformation temperature, and even generate a synergistic effect when the cyclodextrin and the derivative are used at the same time, wherein the content of hydroxypropyl-beta-CD: the combination of calcium phthaloyl glycinate ═ 3:1 "gives rise to excellent effects which are difficult to predict.
The above-mentioned embodiments are only preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, several modifications can be made without departing from the present invention, and these should also be considered as within the scope of the present invention.
Claims (2)
1. The polypropylene plastic containing the composite nucleating agent is characterized in that the composite nucleating agent consists of an inclusion compound of cyclodextrin and derivatives thereof and a synergist, the synergist is phthalic acid calcium glycinate, the inclusion compound of the cyclodextrin and the derivatives thereof is selected from hydroxypropyl-beta-cyclodextrin inclusion compounds, the weight ratio of the inclusion compound of the cyclodextrin and the derivatives thereof to the synergist is 3:1, the weight ratio of the isotactic polypropylene to the composite nucleating agent is 100:0.05-0.5, and the raw material of the polypropylene plastic also contains an antioxidant and/or an anti-ultraviolet agent.
2. The preparation method of the polypropylene plastic as claimed in claim 1, wherein the isotactic polypropylene, the composite nucleating agent, the antioxidant and/or the anti-ultraviolet agent are put into a stirrer according to a specified proportion, are uniformly stirred and then are granulated by a granulator at 185 ℃, and are injection molded at 200 ℃ after the granules are dried to obtain the polypropylene plastic.
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| CN201710574771.5A CN107325403B (en) | 2017-07-14 | 2017-07-14 | Polypropylene plastic containing composite nucleating agent and preparation method thereof |
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| CN201710574771.5A CN107325403B (en) | 2017-07-14 | 2017-07-14 | Polypropylene plastic containing composite nucleating agent and preparation method thereof |
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| CN107325403B true CN107325403B (en) | 2022-03-18 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114656693B (en) * | 2021-04-15 | 2023-06-23 | 上海齐润新材料有限公司 | Nucleating agent and product thereof |
| CN113429496A (en) * | 2021-07-09 | 2021-09-24 | 贵州大学 | Application of modified anhydrous beta-cyclodextrin as polypropylene foaming nucleating agent |
| CN115286840B (en) * | 2022-08-05 | 2024-04-16 | 中化石化销售有限公司 | Sorbitol compound nucleating agent, polypropylene material, preparation method and application thereof |
| CN117164932B (en) * | 2023-10-31 | 2024-01-26 | 汕头市虹桥包装实业有限公司 | Injection molding foaming polypropylene material, preparation method thereof and application thereof in lightweight high-performance bottle cap |
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- 2017-07-14 CN CN201710574771.5A patent/CN107325403B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Nucleation Effect of Cyclodextrin Inclusion Compounds on the Crystallization of Polypropylene;CHUN LI et al;《Journal of Polymer Science：Part B：Polymer Physics》;20090115;第47卷(第2期);第130-137页 * |
| 邻苯二甲酰甘氨酸钙对等规聚丙烯性能的影响;刘曙东 等;《塑料》;20170218;第46卷(第1期);第12-14、18页 * |
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