CN1034741A - High workability high-toughness polypropylene plastics and preparation thereof - Google Patents
High workability high-toughness polypropylene plastics and preparation thereof Download PDFInfo
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- CN1034741A CN1034741A CN 88100052 CN88100052A CN1034741A CN 1034741 A CN1034741 A CN 1034741A CN 88100052 CN88100052 CN 88100052 CN 88100052 A CN88100052 A CN 88100052A CN 1034741 A CN1034741 A CN 1034741A
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Abstract
The invention belongs to high workability high-toughness polypropylene engineering plastics and method for making thereof.Use blend technique, with acrylic resin, organo-peroxide or contain polypropylene cooling masterbatch and the ethylene-propylene rubber(EPR) and the composite nucleating agent blend of micro-superoxide, prepare and have the impact-resistant polypropylene engineering plastics of high workability, the IZOd impact value of its melting index and+23 ℃ was respectively the 5-45 gram/10 minutes and the 5-65 kilogram.Cm/can satisfy the moulding and the service requirements of the complex-shaped large thin-wall goods of preparation.
Description
The invention belongs to impact-resistant polypropylene engineering plastics of high workability and preparation technology.
Polypropylene is one of five big general-purpose plastics, is mainly used in preparation fiber, film and general plastics.More and more pay attention to replacing some metal parts in fields such as automotive industry and household electrical appliance industry in recent years with engineering plastics.Wherein the most valued is the polypropylene engineering plastics, because advantage such as that it has is inexpensive, chemically stable, water-fast and easy processing.
The plastic components that adopts in automobile or the household electrical appliance industry has that the multiple shape of shape, wall are thin, the characteristics of integration and maximization.These polypropylene engineering plastics that just require to prepare these parts have higher flowability and impelling strength.Because consider that from the angle of processing and forming technology having the high-flowability polypropylene engineering plastics can once be injection molded into large complicated plastic components on injection molding apparatus, improved processing characteristics.Consider that from the use properties angle of parts the polypropylene engineering plastics with high impact toughness can resist the destruction of foreign impacts power, member of imparting excellent mechanical property.
Generally speaking, the flowability that had of general purpose polypropylene resin and impelling strength can not satisfy the processing and forming technology and the use properties requirement of the plastic components in preparation automotive industry and the household electrical appliance industry.Essential through modification, improve the processing characteristics and the impelling strength of resin, just have practical value.The processing flowability that improves resin is that hydrogen is regulated method and Chemical Regulation method industrial widespread use.So-called hydrogen adjusting method is in the polypropylene polymerization process highly purified hydrogen to be fed the polypropylene polymerization reaction kettle, hydrogen and catalyst active center's reaction, stop the further growth of polypropylene chains, regulate the promptly mobile purpose of molecular weight thereby reach, the shortcoming of this method is the product molecular weight distribution broad, and to the facility investment height.
The Chemical Regulation method is that a spot of chemical reagent is added in polypropylene powder or the pellet, chemical reagent and polypropylene molecular chain interact under molten state, produce chemical reaction, make the polypropylene molecule splitting of chain, reduce the molecular resin amount, reach and improve mobile purpose.External existing report that superoxide improves the acrylic resin flowability and the patent (Angew, Makromol, Chem, 1980,8941 and GerPat1,495,285) utilized.Its impelling strength obviously descends behind the resin flow property improvement.In acrylic resin, disperse a small amount of toughner can improve the toughness of resin equably.Industrial common method has chemical copolymerization method and mechanical blending method.Chemical copolymerization method is in the polypropylene polymerization process a certain amount of properties-correcting agent monomer to be fed in the polymerization reaction kettle, under the effect of catalyzer, the polyreaction that the properties-correcting agent monomer participates in propylene forms multipolymer, and this method is owing to relate to complicated polymerization technique process, and the facility investment expense is higher.Therefore common employing mechanical blending method is improved polyacrylic impelling strength with the rubber of ethylene-propylene rubber(EPR) or other types, but after adding ethylene-propylene rubber(EPR), the flowability of polypropylene blend reduces, and process industrial art performance is poor.(clear 85-71,652, Polymer EngSCi198222536).There is patent (clear 51-139845) to report with organo-peroxide and ethylene-propylene rubber(EPR) with the mechanical blending modified polypropene but the melting index of the plastics that obtain and corresponding resistance to impact shock still do not have high workability that ideal adds man-hour and the toughness that is suitable for.
The objective of the invention is to prepare a kind of polypropylene engineering plastics with the good and impelling strength of processing characteristics.In the mechanical blending process, by control add an amount of flowing regulator and plasticized modifier in the acrylic resin to reach at relative broad range inner control polypropylene engineering plastics in the flowability of the course of processing with improve the impelling strength of goods, thereby can be used for preparing the plastics of complex-shaped large thin-wall, satisfy and use polypropylene engineering plastics component processing moulding and service requirements in the fields such as automotive industry and household electrical appliance industry.
Decomposition based on organo-peroxide can cause the molecular chain chain rupture of acrylic resin and improve its flowability, adds composite nucleating agent, improves the basic crystallization behavior of polypropylene and increases nucleus number, refinement spherocrystal; With the rubber particles properties-correcting agent that is dispersed in resin matrix when being subjected to the foreign impacts stress, properties-correcting agent can cause in the matrix producing a large amount of little crazings, absorbs the foreign impacts energy, reaching increases the flexible purpose.The preparation method of polypropylene engineering plastics of the present invention is to be matrix resin with the acrylic resin, control adds an amount of organo-peroxide and improves the melting index of resin and composite nucleating agent, an amount of ethylene-propylene rubber(EPR) plasticized modifier and other auxiliary agents as fluidity regulator, in the screw type blender, carry out abundant blend, prepared the polypropylene engineering plastics that have at the high impact-resistant of high workability that adds man-hour and goods.Polypropylene engineering plastics by the inventive method preparation have comparatively ideal injection molding process performance and shock resistance destructive ability, can be used to prepare the large scale plastic product of different shape complexity.
The matrix resin that the present invention adopts is an acrylic resin, and it can be the homopolymer of propylene, also can be the segmented copolymer of propylene and ethene.The weight content of ethene is less than or equal to 45% in the ethylene-propylene block copolymer that the present invention adopts.
The organo-peroxide weight content scope that the present invention adopts is at 0.03-1 part/100 part resin, and the melting index scope of the acrylic resin after the modification is 5-60.The organo-peroxide that adopts has: tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, peroxidized t-butyl perbenzoate and 2, two (tert-butyl peroxy base) hexanes of 5-dimethyl-25-etc.The organo-peroxide that the present invention adopts can add as fluidity regulator with the polypropylene cooling masterbatch that contains micro-organo-peroxide (development of new techniques company of chemistry institute of Chinese Academy of Sciences merchandising), polypropylene cooling masterbatch is 5-35 part/100 part in the weight content scope of acrylic resin, and the variation range of the melting index of the acrylic resin after the modification is between 5-60.The content of polypropylene cooling masterbatch and dicumyl peroxide to the influence of the melting index of homopolymer polypropylene and ethylene-propylene block copolymer (weight content of ethene is 30%) as depicted in figs. 1 and 2.The free radical that decompose to produce owing to organo-peroxide causes polypropylene to produce DeR making polyethylene produce crosslinking reaction, thereby the content of ethene has tangible influence to the change of melting index in the acrylic resin.On preparation technology, adopt polypropylene cooling masterbatch to compare and directly organo-peroxide is joined the safer and convenience of operation in the acrylic resin as flow modifier.
Composite nucleating agent of the present invention is made up of hexanodioic acid and Sodium Benzoate, and its weight proportion is 5-100: 100-5, and the add-on of composite nucleating agent in 100 parts of modified polypropylene resins is 0.2-1 part (weight).
The plasticized modifier ethylene-propylene rubber(EPR) that adopts among the preparation method of the present invention, for overcoming pure ethylene-propylene rubber(EPR) particle self-adhesion and being difficult for the dispersive shortcoming, operating procedure is convenient, and the dispersiveness of the ethylene-propylene rubber(EPR) in the rubber grain grain in acrylic resin is better with the high-flowability polypropylene resin alloy time, with ethylene-propylene rubber(EPR) (molar content of therein ethylene is 25-80%) and acrylic resin blend, make rubber master batch, wherein ethylene-propylene rubber(EPR) and acrylic resin or ethylene-propylene block copolymer proportioning are 30-70: the 70-30(weight part), best proportioning is 50: the 50(weight part).Rubber master batch (ethylene-propylene rubber(EPR)/ethylene-propylene block copolymer is 50/50) content to the influence of Izod (IZod) shock strength of polypropylene engineering plastics and melting index as shown in Figure 3.
The mechanical blending equipment that the present invention adopts is single screw rod or double-screw type blend forcing machine.Through a blend or twice stepwise Co-mixturing, 23 ℃ of Izods (IZod) impact value of preparing the polypropylene engineering plastics is in 5-65 kilogram cm/under molten state, and has processing flowability preferably.
The present invention adopts the preparation method of mechanical blending to have than chemical modification method in propylene polymerization processes does not increase equipment, the advantage of less investment, especially domestic existing acrylic resin kind just can directly make high workability and shock resistance destructive engineering plastics with method of the present invention, and is easy to utilize.Its melting index of polypropylene engineering plastics that makes with the inventive method and+23 ℃ of Izod impact values down are respectively within 5-45 gram/10 minutes and the 5-65 kilogram cm/.Thereby applied range, be applicable to the various maximizations of preparation, thin-walled property, the plastic components of complicated and integration.The mobile improvement and the adding of nucleator also impel in the production process of plastic components and have shortened shaping cycle, are suitable for scale operation, have improved throughput.The raising of shock resistance destructiveness has improved the use properties of plastics, has prolonged work-ing life.Compare with import Japan polypropylene resin and under identical melting index, to have higher Izod shock strength (subordinate list 1), but therefore with the inventive method modification home-made acrylic resin import substitution acrylic resin.And shock resistance is better than the import acrylic resin.
Japanese import polypropylene of table 1 and modified polypropylene resin KH-M-15 of the present invention
And the KH-M-9 performance relatively
The preparation of example 1. rubber master batch
Prescription:
100 kilograms in ethylene-propylene rubber(EPR) (propylene content 0.3 (weight))
100 kilograms of ethylene-propylene block copolymers (propylene content 0.7 (mole))
Antioxidant 1010 50 grams
Preparation:
Ethylene-propylene rubber(EPR) is cold-pressed into the thick sheet rubber of 0.5cm on twin-roll machine, is cut into the rubber grain with rotary rubber dicing machine again.By prescription rubber grain polypropylene granules and antioxidant 1010 are mixed,, promptly obtain rubber master batch again in single screw extrusion machine blend and granulation.
Blending condition is:
The single screw extrusion machine of screw diameter=20 millimeter; Length-to-diameter ratio 20,
Controlled temperature is: 200 ℃ (head), 230 ℃, 230 ℃ and 180 ℃ (opening for feed);
Screw speed: 120 rev/mins
The preparation of the poly-property modified polypropylene resin of example
100 kilograms of ethylene-propylene block copolymers (propylene content 0.7 (mole))
18 kilograms of polypropylene cooling masterbatch
Antioxidant 1010 50 grams
Preparation:
In mixing tank, will mix blend in single screw extrusion machine again by the raw material of formulated.Blending condition is identical with example 1.Extrude also and promptly obtain the high-flowability polypropylene resin after the granulation.Adopt ASTM D1238-79 plastics melting index (MI) bioassay standard under the weight of 230 ℃ and 2.16 kilograms, record its MI=30.
The preparation of example 3. modified polypropylene resins
Prescription:
100 kilograms of acrylic resins
10 kilograms of polypropylene cooling masterbatch
Antioxidant 1010 50 grams
The MI=29 that preparation and test obtain the acrylic resin of this prescription according to the preparation method and the MI measuring method of example 2
The preparation of example 4. modified polypropylene resins
Prescription:
100 kilograms of ethylene-propylene block copolymers
Dicumyl peroxide 400 grams
Antioxidant 1010 50 grams
Preparation and test:
According to the preparation method of example 2 and the measuring method of MI, obtain the MI=22 of the acrylic resin of this prescription.
The preparation of example 5. high workability high-toughness polypropylene engineering plastics.
Prescription:
100 kilograms of modified polypropylene resins (MI=30)
20 kilograms of rubber master batch
Composite nucleating agent 200 grams
Anti ultraviolet agent (uv-531) 20 grams
Static inhibitor (HE-1) 20 grams
Preparation and test:
According to the preparation method of example 2, can obtain its MI=10 of high workability high-toughness polypropylene engineering plastics, the shock strength that is determined under 23 ℃ by ASTMD256-78 plastics cantilever Beam shock strength (Izod shock strength) method is 20 kilograms of cm/.
The preparation of example 6. high workability high-toughness polypropylene engineering plastics.
Prescription:
100 kilograms of modified polypropylene resins (MI=30)
10 kilograms of rubber master batch
Composite nucleating agent 200 grams
Anti ultraviolet agent (uv-531) 20 grams
Static inhibitor (HE-1) 20 grams
Preparation and test:
According to the preparation and the measuring method of example 5, the shock strength of the polypropylene engineering plastics that obtain is 11.4 kilograms of cm/, melting index MI=15.
The preparation of example 7. high workability high impact toughness polypropylene engineering plastics
100 kilograms of ethylene-propylene block copolymers (ethylene content 0.7 (mole))
17 kilograms of polypropylene cooling masterbatch
Composite nucleating agent 200 grams
17.5 kilograms of rubber master batch
Antioxidant 1010 50 grams
Preparation and test:
According to the preparation and the measuring method of example 5, the shock strength of the polypropylene engineering plastics that obtain is 11.1 kilograms of cm/(23 ℃) and melting index MI=15.
The preparation of example 8. high workability high impact toughness polypropylene engineering plastics
100 kilograms of modified polypropylene resins
20 kilograms of rubber master batch
Composite nucleating agent 200 grams
Anti ultraviolet agent (uv-531) 20 grams
Static inhibitor (HE-1) 20 grams
Preparation and test:
In mixing tank, will mix blend in twin screw extruder again by the raw material of formulated.The performance perameter that the blend twin screw is extruded is as follows:
Screw diameter (φ): 30 millimeters
Length-to-diameter ratio is: 90
Blending condition is:
Controlled temperature is: 200 ℃ (head), 220 ℃, 230 ℃ 230 ℃ 180 ℃ (import).
Screw speed: 150 rev/mins.
Melting index and the shock strength of measuring the polypropylene engineering plastics of preparation according to ASTM D1338-79 and D256-78 testing standard respectively are 11 and 23 kilograms of cm/.
The preparation of example 9. high workability high impact toughness polypropylene engineering plastics
Prescription:
100 kilograms of modified polypropylene resins (MI=45)
25 kilograms of rubber master batch
Composite nucleating agent 200 grams
Preparation and test:
According to the preparation and the testing method of example 8,23 ℃ of following Izod shock strengths that obtain the polypropylene engineering plastics are 9.2 kilograms of cm/and melting index MI=25.
Claims (5)
1, a kind of polypropylene engineering plastics that contain ethylene-propylene rubber(EPR), the blend of the composite nucleating agent that it is characterized in that containing melting index with the organo-peroxide modification and be/10 minutes acrylic resin of 5-60 gram and be matrix resin and form by hexanodioic acid and Sodium Benzoate, the weight proportion of hexanodioic acid and Sodium Benzoate is 5-100: 100-5 in the described compound nucleus agent, contains (weight part) in the blend:
Modified polypropylene resin (melting index 5-60 gram/10 minutes) 100
Composite nucleating agent 0.2-1
Ethylene-propylene rubber(EPR) 5-30.
2, a kind of method for preparing the described polypropylene engineering plastics of claim 1 is characterized in that:
The 70-30(weight part) and oxidation inhibitor fully blend in the screw type blender (a) ethylene-propylene rubber(EPR) and acrylic resin are pressed 30-70:, blending temperature is 180-230 ℃, the preparation rubber master batch, the best proportioning of ethylene-propylene rubber(EPR) and acrylic resin is 50: the 50(weight part)
(b) organo-peroxide and the oxidation inhibitor that adds 0.03-1 part (weight) in the acrylic resin of 100 parts (weight) is pressed the blend of (a) condition, and making melting index is/10 minutes modified polypropylene resin of 5-60 gram,
(c) rubber master batch that (a) made and the modified polypropylene resin that (b) makes and composite nucleating agent and oxidation inhibitor, anti ultraviolet agent, static inhibitor, oleylamide by the blend of (a) condition, make high workability and impact polypropylene engineering plastics by prescription.
3, preparation method as claimed in claim 2, it is characterized in that organo-peroxide can be the cooling masterbatch that contains organo-peroxide in (b), its consumption is the polypropylene cooling masterbatch that adds 5-30 part (weight) in 100 parts of (weight) acrylic resins.
4, as claim 2 or 3 described preparation methods, it is characterized in that the screw type blender in (a) is a single-bolt type, also can be double-screw type.
5, as claim 2 or 3 or 4 described preparation methods, it is characterized in that acrylic resin, organo-peroxide, ethylene-propylene rubber(EPR) master batch, composite nucleating agent and oxidation inhibitor, anti ultraviolet agent, static inhibitor, oleylamide once by the condition blend of (a), are made high workability impact polypropylene engineering plastics by prescription.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100052 CN1009105B (en) | 1988-01-14 | 1988-01-14 | Polypropylene with high fluidity and toughness and the prodn. thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100052 CN1009105B (en) | 1988-01-14 | 1988-01-14 | Polypropylene with high fluidity and toughness and the prodn. thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034741A true CN1034741A (en) | 1989-08-16 |
| CN1009105B CN1009105B (en) | 1990-08-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100052 Expired CN1009105B (en) | 1988-01-14 | 1988-01-14 | Polypropylene with high fluidity and toughness and the prodn. thereof |
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| Country | Link |
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| CN (1) | CN1009105B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429308B (en) * | 2007-11-08 | 2011-04-20 | 中国石油天然气股份有限公司 | Process for producing polypropylene degradation master batch |
| CN103265758A (en) * | 2013-06-03 | 2013-08-28 | 四川大学 | Preparation method for low temperature toughness isotatic polypropylene product |
| CN108641375A (en) * | 2018-04-29 | 2018-10-12 | 徐菡 | Wear-resisting PP plastics of a kind of high flowing and preparation method thereof |
| CN113372613A (en) * | 2021-06-21 | 2021-09-10 | 万华化学(四川)有限公司 | Composite modifier for reducing melt index of polypropylene, preparation method and application thereof, and granulation process of high melt index polypropylene |
| CN115418055A (en) * | 2022-10-17 | 2022-12-02 | 北京天罡助剂有限责任公司 | High-fluidity polypropylene plastic and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425646C (en) * | 2005-01-18 | 2008-10-15 | 洛阳石化聚丙烯有限责任公司 | Polypropylene resin composition for hot channel injecting formation and production thereof |
-
1988
- 1988-01-14 CN CN 88100052 patent/CN1009105B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429308B (en) * | 2007-11-08 | 2011-04-20 | 中国石油天然气股份有限公司 | Process for producing polypropylene degradation master batch |
| CN103265758A (en) * | 2013-06-03 | 2013-08-28 | 四川大学 | Preparation method for low temperature toughness isotatic polypropylene product |
| CN103265758B (en) * | 2013-06-03 | 2015-07-29 | 四川大学 | A kind of preparation method of low-temperature flexibility isotatic polypropylene goods |
| CN108641375A (en) * | 2018-04-29 | 2018-10-12 | 徐菡 | Wear-resisting PP plastics of a kind of high flowing and preparation method thereof |
| CN113372613A (en) * | 2021-06-21 | 2021-09-10 | 万华化学(四川)有限公司 | Composite modifier for reducing melt index of polypropylene, preparation method and application thereof, and granulation process of high melt index polypropylene |
| CN113372613B (en) * | 2021-06-21 | 2022-07-12 | 万华化学(四川)有限公司 | Composite modifier for reducing melt index of polypropylene, preparation method and application thereof, and granulation process of high melt index polypropylene |
| CN115418055A (en) * | 2022-10-17 | 2022-12-02 | 北京天罡助剂有限责任公司 | High-fluidity polypropylene plastic and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1009105B (en) | 1990-08-08 |
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