CN101724195A - Polypropylene composition and preparation method thereof - Google Patents
Polypropylene composition and preparation method thereof Download PDFInfo
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- CN101724195A CN101724195A CN200810224875A CN200810224875A CN101724195A CN 101724195 A CN101724195 A CN 101724195A CN 200810224875 A CN200810224875 A CN 200810224875A CN 200810224875 A CN200810224875 A CN 200810224875A CN 101724195 A CN101724195 A CN 101724195A
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Abstract
The invention provides a polypropylene composition and a preparation method thereof, relating to a technique of nucleating agent polypropylene resin. The composition comprises mixed polypropylene resin and compound powder rubber with the weight ratio of (0.01-2):100, wherein the compound powder rubber is powder silicon rubber compounded with nucleating agent having the average grain diameter of 20-1000nm; the rubber phase gel content in the compound powder rubber is more than or equal to 60 percent by weight, and the weight ratio of the rubber phase and the nucleating agent is 99:1 to 10:90. The compound powder rubber is prepared by mixing silicon rubber latex via irradiation vulcanization and water solution or emulsion of organophosphates nucleating agent according to the needed dry weight ratio, evenly stirring and drying. The polypropylene composition has good rigidity and obtains high heat deflection temperature and processing performance as the rubber phase in the powder silicon rubber with nucleating agent and the nucleating agent can be evenly dispersed in the polypropylene matrix.
Description
Technical field
The present invention relates to a kind of polypropene composition, say further, relate to nucleater modified polypropene composition and preparation method thereof.
Background technology
Polypropylene (PP) have good mechanical property, nontoxic, relative density is low, heat-resisting, chemicals-resistant, be easy to advantages such as machine-shaping, and is and cheap.This resin can be the preferred kind that replaces engineering plastics by processing modified its outstanding physical and mechanical properties of giving.Polypropylene is being obtained very big progress in recent years aspect the general-purpose plastics through engineering approaches, be the fastest, the most active kind of new varieties of rate of growth in the five big general synthetic resins.By in polypropylene, adding a spot of nucleator, can change polyacrylic crystal habit, realize the improvement of physical and mechanical properties such as polypropylene rigidity, toughness, heat-drawn wire, creep property, the transparency and product surface glossiness and processing characteristics, thereby improve the use properties of goods, widen range of application.
Begin to realize the commercialization of transparent PP abroad from the eighties in 20th century.China now has produced in small quantities from beginning to develop the nucleator product around the early 1990s.Along with the fast development of China's plastics industry and the progressively in-depth that nucleator is familiar with, in recent years, nucleator just more and more receives publicity as the research of the functionalization auxiliary agent of polypropylene modification.At present, the usage quantity of China's nucleator increases sharply, and nucleator market starts.But on the nucleator impact of performance, still need improve.
Xu Runhua is published in and has introduced present crystalling propylene theory and nucleator function, classification in the article " polypropylene nucleater research and development progress " of Henan chemical industry on 2003 the 6th phases.Polypropylene nucleater is divided into inorganic nucleator, organic nucleating agent and polymer nucleator substantially at present.Wherein inorganic nucleator comprises talcum powder, lime carbonate, silicon-dioxide etc., and characteristics are wide material sources, and are cheap; But nucleating effect is not good, and is poor with resin compatible.The polymer nucleator is to have the polymkeric substance higher with the fusing point of polyolefine similar structures, adds before the polyolefin resin polymerization usually, is dispersed in the resin matrix in polymerization process.At first crystallization in the resin melt process of cooling.Be characterized in that the synthetic of nucleator finish in synthetic simultaneously with being engaged in resin, can be dispersed in the resin.Organic nucleating agent is the commonly used and effect of a class nucleator preferably, mainly comprises lipid acid and metallic soap class thereof, dibenzal sorbitol class and organic phosphate.The nucleator in organic phosphate class effect is better, but dispersed relatively poor in the acrylic plastering matrix, price is higher.
Summary of the invention:
The inventor finds through a large amount of experiments, with silicon rubber powder and organophosphorus compounds nucleator composite after, carry out melt blending with polypropylene, the silicon rubber powder of compound nucleator can help the dispersion of nucleator in polypropylene matrix, can prepare the polypropylene of Gao Gang, high heat distortion temperature.And the shear viscosity of this modified polypropene compares decline with existing commercially available pure nucleater modified polypropylene, helps the processing of polypropylene product.The cost of the silicon rubber powder of this compound nucleator is starkly lower than existing nucleator.
Therefore, the purpose of this invention is to provide a kind of polypropene composition that contains composite powder rubber.It has favorable rigidity, thermotolerance and processing characteristics.
Another object of the present invention provides the preparation method of described polypropene composition.
A kind of polypropene composition of the present invention, it includes the following component of blend: acrylic resin and composite powder rubber.
Above-described acrylic resin comprises the disclosed various types of acrylic resins of prior art, comprises homo-polypropylene and Co-polypropylene etc.The ratio of composite nucleating agent gross weight and acrylic resin gross weight is (0.01～2): 100, be preferably (0.01～1): and 100, more preferably (0.01～0.8): 100.
The above composite powder rubber has been meant the silicon rubber powder of nucleator compound, can and get by the method preparation that includes one of following steps:
A. the aqueous solution that nucleator is mixed with or emulsion or the night that suspends;
B. adding or not adding under the situation of crosslinking coagent, adopt the energetic ray source to carry out radiation vulcanization silicone rubber latex; Again the aqueous solution of nucleator or the rubber latex behind emulsion and the irradiation are mixed, obtain mixed emulsion, afterwards with this mixed emulsion drying.
In the above polypropene composition of the present invention in the silicone rubber latex described in the preparation method of composite powder rubber in the weight of institute's silicon rubber (being the solid content of silicone rubber latex dry weight or silicone rubber latex) and the nucleator aqueous solution or the emulsion ratio of the weight (solution or emulsion dry weight) of contained nucleator be 99: 1～10: 90, be preferably 95: 5～20: 80, more preferably 90: 10～20: 80.
Above-described nucleator is the organophosphorus compounds nucleator, i.e. (replacement) aryl phosphate ester salt.Preferred two (4-tert-butyl-phenyl) phosphoric acid ester sodiums (NA-10), methylene-bis (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester sodium (NA-11), methylene-bis (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester oxyaluminum salt (NA-21).Can be in composite powder method for preparing rubber of the present invention according to ordinary method with solution or emulsion or the suspension use that is mixed with water soluble in water of organophosphorus compounds nucleator.
In the preparation method of the composite powder rubber of polypropene composition of the present invention, the solution of nucleator or emulsion can be added while stirring in the silicone rubber latex behind the irradiation, make it to mix through fully stirring.The concentration of silicone rubber latex and the concentration of nucleator solution or emulsion are had no special requirements.Wherein the solid content of silicone rubber latex (drc) generally can be 20～70% weight, is preferably 30～60% weight, more preferably 40～50% weight.
Silicone rubber latex raw material unanimity described in the described silicone rubber latex of preparation method of the contained composite powder rubber of polypropene composition of the present invention and the Chinese patent ZL01801656.1 (its priority patent is 00109217.0, June 15 2000 priority application day).Be that described silicone rubber latex is the emulsion of lower molecular weight organosilicon polymer or multipolymer, be preferably silicone oil emulsion, all can pass through commercially available getting.
In the preparation method of the contained composite powder rubber of polypropene composition of the present invention, the drying means that adopts in the described drying process is with the drying means of preparation during fully sulfurized silicon rubber powder among the Chinese patent ZL01801656.1, be that drying process can be carried out with spray-dryer, inlet temperature can be controlled at 100～200 ℃, and temperature out can be controlled at 20～80 ℃.
Among preparation method's step b of the contained composite powder rubber of polypropene composition of the present invention, for the irradiance method of silicone rubber latex irradiance method with preparation fully sulfurized silicon rubber powder among the Chinese patent ZL01801656.1.In silicone rubber latex, crosslinking coagent can be do not used, also crosslinking coagent can be used.Used crosslinking coagent is selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent or polyfunctional group crosslinking coagent and arbitrary combination thereof.The example of described simple function group crosslinking coagent includes, but is not limited to: (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; The example of described two functional group's crosslinking coagents includes, but is not limited to: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Vinylstyrene; The example of described trifunctional crosslinking coagent includes, but is not limited to: trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate; The example of described four-functional group crosslinking coagent includes, but is not limited to: tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane four (methyl) acrylate; The example of described polyfunctional group crosslinking coagent includes, but is not limited to: Dipentaerythritol five (methyl) acrylate.In this article, " (methyl) acrylate " refers to acrylate or methacrylic ester.These crosslinking coagents can use in the mode of arbitrary combination, as long as they help sulfuration under irradiation.
The add-on of the above crosslinking coagent is generally the 0.1-10% weight of dried glue weight in the silicone rubber latex, is preferably 0.5～9% weight, more preferably 0.7～7% weight.
The energetic ray source is selected from cobalt source, ultraviolet or high-energy electron accelerator among preparation method's step b of the contained composite powder rubber of polypropene composition of the present invention, preferred cobalt source.Irradiation dose should make that the gel content of rubber reaches 60% weight or higher, preferred 75% weight or higher, most preferably 80% weight or higher behind the silicone rubber latex radiation vulcanization.The dosage of irradiation can be 0.1～40Mrad, preferred 0.5～30Mrad.
The composite powder rubber that above method obtains be with the mixing behind the cross-linking radiation silicone rubber latex of nucleator emulsion or solution obtain after drying, because used nucleator is a low molecular compound, so the influence to rubber particles in the rubber latex is very little, the particle diameter of the composite powder rubber that obtains after the drying and former latex particle diameter are basic identical, still keeping median size is 20～1000nm, be preferably 50～500nm, more preferably 50～200nm.
Generally speaking by the gel content of the contained rubber phase of the composite powder rubber of described method gained consistent with the gel content of silicone rubber latex behind the irradiation, so the gel content of rubber phase is 60% weight or higher in the composite powder rubber of the present invention, preferred 75% weight or higher, most preferably 80% weight or higher.The weight ratio of rubber phase and nucleator is 99: 1～10: 90 in the described composite powder rubber, is preferably 95: 5～20: 80, more preferably 90: 10～20: 80.
Composite powder rubber in the above-described polypropene composition of the present invention, in the composition that itself and acrylic resin blend obtain, silicon rubber in the composite powder rubber and nucleator are dispersed in the acrylic resin, because the existence of powdered rubber disperses nucleator in polypropylene matrix more even, powdered rubber and nucleator can produce certain synergistic effect, obtain nucleator effect preferably, be better than the nucleating effect of the nucleator of use separately.Polyacrylic rigidity and heat-drawn wire are obviously improved, and be better than the effect of the nucleator of independent use.And the polypropylene shear viscosity is descended, help processing.
Can also include some auxiliary agents commonly used in the polypropylene course of processing such as oxidation inhibitor etc. in the composition of polypropene composition of the present invention, its consumption is conventional amount used, or adjusts according to practical requirements.
The preparation method of polypropene composition of the present invention comprises that the component that will include described acrylic resin and described composite powder rubber according to the step of described content by melt blending, makes described polypropene composition.Normally all components is mixed earlier, carry out melt blending then.
In the preparation process of polypropene composition of the present invention, material melt blending temperature is used blending temperature in the common polypropylene processing, can decide according to the polypropylene fusion temperature, should select not only guaranteeing the complete fusion of polypropylene matrix plastics but also can not make in the scope of its decomposition, be generally 160 ℃～240 ℃.In addition, according to the processing needs, can add some auxiliary agents commonly used in the polypropylene course of processing such as oxidation inhibitor etc. in right amount in the blend material, its consumption is conventional amount used, or adjusts according to practical requirements.
The blending equipment of mixing of materials can adopt various mixing equipments used in the prior art in the preparation method of the invention described above, as stirrer, kneading machine etc.Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in the method for the invention described above, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
Polypropene composition of the present invention, because rubber phase and nucleator component homodisperse in the acrylic resin matrix in the composite powder rubber, silicon rubber powder and organophosphate nucleator can produce certain synergistic effect, can make acrylic resin have favorable rigidity, high heat distortion temperature and good processing properties, and can make the cost that reduces independent use nucleator.
Description of drawings
Embodiment:
Below in conjunction with embodiment, further specify the present invention.
The testing method of shear viscosity: adopt the polyacrylic shear viscosity of GOTTFERT capillary rheometer determining.Probe temperature is 190 ℃, and length capillaceous and diameter are respectively 20mm and 0.5mm, has ignored end effect in the experiment, but adopts the Rabinowitsch bearing calibration that experimental result is proofreaied and correct.
With solid content is that commercially available methylol silicone oil emulsion (Beijing company of section produce, the trade mark KH-L10) 5Kg of 30% weight places container, under agitation drips Viscoat 295 75g, after being added dropwise to complete, continues to stir one hour.Use cobalt-60 radiosterilize afterwards, dosage is 20Mrad, and dose rate is 50Gy/min.After the irradiation in the latex gel content of silicon rubber particle be 81.0%, average particle size is 150nm.With nucleator NA-11 (methylene-bis (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester sodium, Japan electric rising sun production) be made into water miscible liquid after, mix by 20: 80 proportionings of dry weight separately with latex after the radiation, stirred 1 hour, and then mixed solution was passed through the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140 ℃-160 ℃, temperature out is 40 ℃-60 ℃, collects dried composite powder rubber 1 in cyclonic separator.Composite powder rubber 1 and (base, the Beijing Chemical Research Institute production of homo-polypropylene powder with above-mentioned gained, melting index 2.6g/10min) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix, it specifically consists of: polypropylene 100 parts by weight, composite powder rubber 1 is that 0.1 parts by weight are (in polypropylene 100 parts by weight, contain nucleator NA-11:0.02 parts by weight), other sneaks in polypropylene and composite powder rubber 1 gross weight is the antioxidant 1010 of 100 part of 0.25 weight part, in high speed agitator, mixed one minute, ZSK-25 twin screw extruder blend granulation with German WP company, each section of forcing machine temperature is respectively 165 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃.(head temperature).Pellet is made the standard batten with injection, and it is as shown in table 1 to obtain after the modification performance of acrylic plastering after tested, and the capillary rheometer determining result as shown in Figure 1.
Embodiment 2
The ratio of the latex after the nucleator NA-11 water miscible liquid among the embodiment 3 and the radiation become according to 80: 20 proportionings of dry weight separately mix, other conditions are prepared composite powder rubber 2 with embodiment 3.The consumption of composite powder rubber 2 is changed into: polypropylene 100 parts by weight, composite powder rubber 2 are 0.05 parts by weight (in polypropylene 100 parts by weight, containing nucleator NA-11:0.04 parts by weight), and all the other are with embodiment 3.Obtained sample is extruded injection moulding and is made the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 1; The capillary rheometer determining result as shown in Figure 1.
Comparative Examples 1
After polypropylene powder among the embodiment 1 and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mixed with 100: 0.25 weight ratio, sample is extruded injection moulding make the standard batten, carry out various Mechanics Performance Testings, the results are shown in table 1; The capillary rheometer determining result as shown in Figure 1.
Comparative Examples 2
Change the composite powder rubber among the embodiment 1 into nucleator NA-11, it specifically consists of: polypropylene 100 parts by weight, nucleator NA-11 is 0.05 parts by weight, and other sneaks in polypropylene and nucleator gross weight is the antioxidant 1010 of 100 part of 0.25 weight part.Other is with embodiment 1, and obtained sample is extruded injection moulding and made the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 1, and the capillary rheometer determining result as shown in Figure 1.
Comparative Examples 3
Nucleator NA-11 content in the Comparative Examples 2 is made into: polypropylene 100 parts by weight, nucleator NA-11 are 0.15 parts by weight, and all the other conditions are all with Comparative Examples 2.Obtained sample is extruded injection moulding and is made the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 1; The capillary rheometer determining result as shown in Figure 1.
Table 1
| Numbering | Tensile strength MPa | Flexural strength MPa | Bending elastic modulus MPa | Heat-drawn wire (0.455MPa) ℃ |
| Testing standard | ?ISO?527：1993 | ??ISO178：2001 | ??ISO178：2001 | ??ISO75：2004 |
| |
?39.7 | ??44.0 | ??2.02 | ??123.8 |
| Embodiment 2 | ?39.2 | ??46.0 | ??2.01 | ??124.1 |
| Comparative Examples 1 | ?38.8 | ??42.4 | ??1.84 | ??121.2 |
| Comparative Examples 2 | ?38.6 | ??42.3 | ??1.94 | ??122.9 |
| Comparative Examples 3 | ?39.0 | ??44.0 | ??1.98 | ??123.0 |
From table 1 and experimental result shown in Figure 1, the polypropene composition by the composite powder modified rubber of the present invention, the polypropene composition more nucleater modified than simple usefulness has better rigidity, high heat distortion temperature and good processing properties.
Claims (9)
1. polypropene composition is characterized in that including the following component of blend: acrylic resin and composite powder rubber; Composite powder rubber has been meant the silicon rubber powder of nucleator compound, and the median size of its particle is 20～1000nm; The weight ratio of rubber phase and nucleator is 99: 1～10: 90 in the described composite powder rubber, and wherein the gel content of rubber phase is 60% weight or higher; Described composite powder rubber is got by the method preparation that includes one of following steps:
A. the aqueous solution that nucleator is mixed with or emulsion or suspension;
B. adding or do not adding under the situation of crosslinking coagent, radiation vulcanization is being carried out in the emulsion employing energetic ray source of lower molecular weight organosilicon polymer or multipolymer; Again the aqueous solution of above-mentioned nucleator or the silicone rubber latex behind emulsion and the irradiation are mixed, obtain mixed emulsion, afterwards with this mixed emulsion drying;
Above-described nucleator is the organophosphorus compounds nucleator;
The ratio of above-described composite powder rubber gross weight and acrylic resin gross weight is (0.01～2): 100.
2. polypropene composition according to claim 1 is characterized in that described composite powder rubber, and the median size of its particle is 50～500nm.
3. polypropene composition according to claim 2 is characterized in that described composite powder rubber, and the median size of its particle is 50～200nm.
4. polypropene composition according to claim 1 is characterized in that the weight ratio of rubber phase and nucleator is 95: 5～20: 80 in the described composite powder rubber.
5. polypropene composition according to claim 1, the gel content that it is characterized in that the rubber phase of described composite powder rubber is 75% weight or higher.
6. polypropene composition according to claim 1, it is characterized in that described nucleator is selected from least a in the following material: two (4-tert-butyl-phenyl) phosphoric acid ester sodium, methylene-bis (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester sodium, methylene-bis (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester oxyaluminum salt.
7. polypropene composition according to claim 1, the gross weight that it is characterized in that described composite powder rubber is (0.01～1) with the ratio of acrylic resin gross weight: 100.
8. polypropene composition according to claim 7, the gross weight that it is characterized in that described composite powder rubber is (0.01～0.8) with the ratio of acrylic resin gross weight: 100
9. preparation method who prepares the described polypropene composition of one of claim 1～8 is characterized in that and will comprise described acrylic plastering and described composite powder rubber makes described polypropene composition in interior component by described amount melt blending.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709496A (en) * | 2012-09-28 | 2014-04-09 | 中国石油化工股份有限公司 | Low-VOC polypropylene composition and preparation method thereof |
| CN103937095A (en) * | 2014-04-02 | 2014-07-23 | 南京淳达科技发展有限公司 | Nucleating agent polypropylene high-performance compound additive and preparation method thereof |
| CN104558820A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Modified polypropylene resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2164461C (en) * | 1994-12-06 | 2000-08-08 | Tatsuya Tanizaki | Polypropylene composition and uses thereof |
| JPH08302099A (en) * | 1995-04-27 | 1996-11-19 | Sumitomo Chem Co Ltd | Polypropylene composition |
| CN1137931C (en) * | 2001-10-12 | 2004-02-11 | 中国石油化工股份有限公司 | Composite powder rubber, its preparation method and application |
| JP2004182955A (en) * | 2002-12-06 | 2004-07-02 | Mitsui Chemicals Inc | Propylene resin composition and use of the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709496A (en) * | 2012-09-28 | 2014-04-09 | 中国石油化工股份有限公司 | Low-VOC polypropylene composition and preparation method thereof |
| CN103709496B (en) * | 2012-09-28 | 2016-02-24 | 中国石油化工股份有限公司 | A kind of low VOC polypropylene composition and preparation method thereof |
| CN104558820A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Modified polypropylene resin and preparation method thereof |
| CN104558820B (en) * | 2013-10-24 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of modified polypropylene resin and preparation method |
| CN103937095A (en) * | 2014-04-02 | 2014-07-23 | 南京淳达科技发展有限公司 | Nucleating agent polypropylene high-performance compound additive and preparation method thereof |
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