CN102234400A - High transparent polypropylene composition and preparation method thereof - Google Patents
High transparent polypropylene composition and preparation method thereof Download PDFInfo
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- CN102234400A CN102234400A CN2010101605022A CN201010160502A CN102234400A CN 102234400 A CN102234400 A CN 102234400A CN 2010101605022 A CN2010101605022 A CN 2010101605022A CN 201010160502 A CN201010160502 A CN 201010160502A CN 102234400 A CN102234400 A CN 102234400A
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Abstract
The invention relates to a high transparent polypropylene composition and a preparation method thereof. The polypropylene composition comprises the following constituents: (a) 100 weight portions of propylene-butylene-1 random copolymers, wherein content of the butylenes-1 is 0.5-7.5 mol%; (b) 0.1-1 weight portions of Millad NX8000 nucleating agents. The composition has the characteristics of high transparency, low transfer object content, high rigidity and high hear resistance, and is suitable for preparing package containers, especially for preparing food and medicine package containers. The preparation method of the composition has the advantages of simple process and low cost.
Description
Technical field
The present invention relates to a kind of polypropene composition and preparation method thereof, more particularly, relate to a kind of polypropene composition and preparation method thereof with low haze, low migration thing content, high rigidity and high heat resistance, said composition is applicable to the preparation packaging vessel, especially food and drug packaging container.
Background technology
Acrylic resin can be by the physical and mechanical propertiess such as adjusting the transparency, rigidity and thermotolerance of cutting out to molecular chain structure.Usually by reducing degree of crystallinity with the ethylene random copolymerization, in conjunction with adding the polypropylene material that the nucleator that can improve the transparency prepares high transparent, often reach the higher transparency by the more comonomer of copolymerization, but this has reduced the degree of crystallinity of material simultaneously, thereby the rigidity and the thermotolerance of material have been reduced, especially the most important thing is to improve the content of noncrystalline part in the material, when being used to pack oil food, the noncrystalline component of part can be moved in food gradually, contaminated food products, stable on heating decline makes it be unfavorable for microwave heating.
Summary of the invention
The present invention finds by great deal of experimental, replace ethene and propylene random copolymerization with butene-1, with the combination of an amount of Millad NX8000 nucleator after, not only strengthened the transparency of material, even if butene-1 content is in lower scope, the transparency of material is still fine, thereby allow us further to reduce the content that moves thing by reducing butene-1 content, can also get both simultaneously superior stiffness and thermotolerance obtain the material that ideal is particularly suited for food and drug packaging.
Therefore, technical problem to be solved by this invention provides a kind of polypropene composition, and said composition has high transparent, low migration thing content, high rigidity and high heat resistance concurrently.
The present invention further provides the preparation method of described polypropene composition, this method technology is simple, cost is low.
Polypropene composition of the present invention includes the following component of blend: (A) propene-1-butene of butene-1 content 0.5～7.5mol%-1 random copolymers, 100 weight parts; (B) Millad NX8000 nucleator, 0.1～1 weight part.
The degree of crystallinity of the butene-1 content meeting impact polypropylene in propene-1-butene-1 random copolymers, butene-1 content is high more, the crystalling propylene degree is low more, and the transparency of material is good more, but butene-1 content is too high, can bring the excessive of migration thing content equally, the too low degree of crystallinity that then can cause of butene-1 content is too high, the influence transparency, and the present invention optimizes butene-1 content 0.5～7.5mol% through test, more preferably 1～6mol%, further preferred 1.5～5mol%.
Different nucleators is different to the raising degree of the polyacrylic transparency, the present invention is directed to the third fourth random copolymers and from numerous nucleators, optimize Millad NX8000 (production of Milliken Chemical company), the consumption of nucleator is 0.1～1 weight part, preferred 0.4～0.6 weight part, more preferably 0.4～0.5 weight part, can when obtaining low migration thing content, obtain the higher transparency and rigidity and thermotolerance.
Composition of the present invention also has following technical characterictic:
(1) melting index (230 ℃/2.16kg) 0.5～50g/10min, preferred 3～30g/10min.
(2) n-hexane extract preferably less than 1.2g/100g, is more preferably less than 1.0g/100g less than 1.5g/100g.
(3) through the sheet material mist degree (1mm thick sheet) of melt injection molding less than 12%, preferably less than 9%, be more preferably less than 7%.
(4) heat-drawn wire is preferably greater than 85 ℃, more preferably greater than 95 ℃ greater than 75 ℃.
(5) modulus in flexure is preferably greater than 1.3GPa greater than 1.1GPa, more preferably greater than 1.5GPa.
Wherein, preferably also have following technical characterictic:
(1) n-hexane extract is less than 1.5g/100g, and less than 7%, heat-drawn wire is greater than 75 ℃ through the sheet material mist degree (1mm thick sheet) of melt injection molding, and modulus in flexure is greater than 1.1GPa.
(2) n-hexane extract is less than 1.2g/100g, and less than 7%, heat-drawn wire is greater than 85 ℃ through the sheet material mist degree (1mm thick sheet) of melt injection molding, and modulus in flexure is greater than 1.3GPa.
(3) n-hexane extract is less than 1.0g/100g, and less than 9%, heat-drawn wire is greater than 95 ℃ through the sheet material mist degree (1mm thick sheet) of melt injection molding, and modulus in flexure is greater than 1.5GPa.
What need to propose is, composition of the present invention is because the n-hexane extract amount is low, and it is low promptly to move thing content, so have more advantage in food product pack, especially oleaginous food product pack.Because the heat-drawn wire height has promptly possessed better thermotolerance simultaneously, be more suitable for microwave heating in addition.
The preparation method of polypropene composition of the present invention comprises: with aforesaid propylene-butene-1 random copolymers powder with comprise that the auxiliary agent of Millad NX8000 nucleator is by above-mentioned weight proportion melt blending.
Wherein, propene-1-butene-1 random copolymers can obtain by the following method:
Ziegler-Natta catalyst exists down, under the polymerization temperature, carries out the copolymerization of propylene and butene-1 under the suitable hydrogen content, obtains the propene-1-butene that MFR is 0.5～50g/10min-1 random copolymers.
Described Ziegler-Natta catalyst is the reaction product of following component basically: (1) is a kind of to be the solid active center component of main ingredient with magnesium, titanium, halogen and internal electron donor; (2) a kind of organoaluminum component; (3) optional one or more external electron donor components; Wherein the ratio between component (1) and the component (2) is counted with aluminium/titanium ratio: 10～500 (weight ratios); If the external electron donor component is arranged, the ratio between organoaluminum and external electron donor component is 2～150 (weight ratios).
Wherein solid active center component (1) includes but not limited to be disclosed in those among Chinese patent CN93102795.0, CN00109216.2, CN200410062291.3, CN200410073621.9, CN200410073623.8, CN200510117429.X, CN200610067177.9, CN200610113863.5, the CN200610113864.X.Catalyzer described in Chinese patent CN93102795.0, CN200410062291.3 and the CN200510117429.X is used for preparation method of polypropylene of the present invention and has advantage especially.
Organoaluminum component (2) wherein, the preferred alkyl aluminum compound, more preferably trialkylaluminium, as: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum etc., wherein the ratio of solids containing titanium active centre component and organoaluminum cocatalyst component is counted with aluminium/titanium ratio: 10～500 (weight ratios).
Wherein external electron donor component (3) is the compound of knowing altogether such as industries such as ether, ester and silane, preferred silane compounds such as methylcyclohexyl dimethoxy silane, dicyclopentyl dimethoxyl silane, second, isobutyl dimethoxy silane (DIB), diisopropyl dimethoxy silane (DIP) etc.
Described three kinds of catalyst components can directly join in the polymerization reactor, also after the pre-complexing and/or prepolymerization that can know altogether through industry, join in the reactor again.Wherein the form of the reactor of pre-complex reaction can be various, its objective is and make each component of catalyzer can obtain fully effectively to mix, can be continuous stirred tank reactor, annular-pipe reactor, contain one section pipeline of static mixer, even also can be the pipeline that one section material is in turbulence state.
The Controllable Temperature of pre-complexing is between-10～60 ℃, and preferred temperature is 0～30 ℃.The time of pre-complexing is controlled at 0.1～180min, and the preferred time is 5～30min.
Through or can also carry out randomly prepolymerization without the catalyzer of pre-complexing and handle.Prepolymerization can be carried out under the liquid phase bulk conditions continuously, also can carry out in the inert solvent discontinuous.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized Controllable Temperature is between-10～60 ℃, and preferred temperature is 0～40 ℃.Prepolymerized multiple is controlled at 0.5～1000 times, and preferred multiple is 1.0～500 times.
Described polyreaction can be in the propylene liquid phase, or carries out in gas phase.When carrying out liquid polymerization, polymerization temperature is 0～150 ℃, with 40～100 ℃ for well; Polymerization pressure should be higher than the saturated vapour pressure of propylene under corresponding polymerization temperature.Polymerization temperature is 0～150 ℃ when vapour phase polymerization, with 40～100 ℃ for well; Polymerization pressure can be a normal pressure or higher, and preferred pressure is 1.0～3.0MPa (gauge pressure, down together).
Polymerization can be to carry out continuously, also may be carried out batchwise.Successive polymerization can one or more placed in-line Liquid-phase reactor or Gas-phase reactor, Liquid-phase reactor can be annular-pipe reactor or stirred-tank reactor, Gas-phase reactor can be horizontal type agitated bed reactor or vertical agitated bed reactor or fluidized-bed reactor etc., and above Liquid-phase reactor and Gas-phase reactor be matched combined at random also.
Among the preparation method of polypropene composition of the present invention, the melt blending temperature of material is used blending temperature in the processing of common polypropylene, should select not only guaranteeing the complete fusion of polypropylene matrix but also can not make in the scope of its decomposition, is generally 180～260 ℃.
Polypropene composition of the present invention can carry out extruding pelletization by use equipment, and described Millad NX8000 nucleator added in the granulation stage.Can add normally used other auxiliary agents in this area during granulation as required, as oxidation inhibitor, photostabilizer, thermo-stabilizer, tinting material etc., consumption is conventional amount used.
Polypropene composition of the present invention compared with prior art has the higher transparency, lower migration thing content, higher rigidity and thermotolerance.Can be used for preparing injection-molded item, especially food and drug packaging container.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Relevant data among the embodiment obtains by following testing method:
1. butene-1 content.The employing method of infrared spectrophotometry is measured, and selects for use wave number at 770cm
-1Absorption peak be the butene-1 characteristic peak, the sample that adopts a series of different butene-1 content is set up typical curve as standard model after measuring butene-1 content with nuclear magnetic resonance spectrometer.
Ethylene content.The employing method of infrared spectrophotometry is measured, and selects for use wave number at 731cm
-1Absorption peak be the ethene characteristic peak, the sample that adopts a series of differing ethylene contents is set up typical curve as standard model after measuring ethylene content with nuclear magnetic resonance spectrometer.
2. n-hexane extract.Pressing GB/T5009.58 measures.
3. melting index (MFR).Press ASTMD1238, measure under 230 ℃, 2.16kg load.
4. modulus in flexure.Pressing ASTM D790 measures.
5. heat-drawn wire (HDT).Pressing ASTM D648 measures.
6. mist degree.Pressing ASTM1003 measures.
Embodiment 1:
Polyreaction is carried out on a cover pilot plant.Its major equipment comprises prepolymerization reactor, first annular-pipe reactor and second annular-pipe reactor.Polymerization process and step are as follows:
(1) prepolymerization reaction:
Primary Catalysts (titaniferous solid active center component) adopts the method that embodiment 1 describes among the Chinese patent CN200410062291.3 (comprising embodiment 1 " preparation magnesium chloride/alcohol adducts particle " and embodiment 1 " the general operation step of preparation spherical catalyst component " before) to obtain, internal electron donor compound wherein adopts n-butyl phthalate, the Primary Catalysts Ti content 2.4wt% that obtains, Mg content 18.0wt%, n-butyl phthalate content 13wt%.
Primary Catalysts, promotor (triethyl aluminum), external electron donor (dicyclopentyl dimethoxyl silane, DCPMS) after the pre-contact of 10 ℃, 20min, add prepolymerization reactor continuously and carry out the prepolymerization reaction, prepolymerization is carried out under propylene liquid phase bulk environment, temperature is 15 ℃, the residence time is about 4min, and the pre-polymerization multiple of catalyzer is about 120-150 times under this condition.The triethyl aluminum flow that advances prepolymerization reactor is 6.33g/hr, and the dicyclopentyl dimethoxyl silane flow is 0.63g/hr, and the Primary Catalysts flow is about 0.01g/hr.
(2) copolymerization of propene-1-butene-1:
The pre-polymerization rear catalyst enters in two placed in-line annular-pipe reactors, finishes the copolymerization of propene-1-butene-1 in annular-pipe reactor.70 ℃ of two endless tube polymeric reaction temperatures, reaction pressure 4.0MPa.The processing condition of gate ring pipe reactor, the productivity ratio that makes first, second endless tube is about 45: 55.
The density of hydrogen that on-line chromatograph detects in the charging of first annular-pipe reactor and second annular-pipe reactor is respectively 3200ppmV and 3050ppmV.
First annular-pipe reactor and the second annular-pipe reactor on-line chromatograph detect butene-1 concentration and are respectively 16mol% and 15mol%.
After the polymkeric substance that comes out from second endless tube goes out propylene through flash separation, remove unreacted activity of such catalysts and heat drying through wet nitrogen again, obtain polymer powders.
In the powder that the polymerization of 100 weight parts obtains, add the nucleator Millad NX8000 (production of Milliken Chemical company) of 0,0.4,0.5 or 0.6 weight part, IRGAFOS 168 additives (Ciba) of 0.1 weight part, IRGANOX 1010 additives (Ciba) of 0.2 weight part and the calcium stearate (Ciba) of 0.05 weight part respectively, use the twin screw extruder granulation.The gained pellet is tested by preceding method.
Embodiment 2:
With embodiment 1, just the density of hydrogen that on-line chromatograph detects in the charging of first annular-pipe reactor and second annular-pipe reactor is respectively 4800ppmV and 4600ppmV, and first annular-pipe reactor and the second annular-pipe reactor on-line chromatograph detect butene-1 concentration and be respectively 5.6mol% and 5.3mol%.
Embodiment 3:
With embodiment 1, just first annular-pipe reactor and the second annular-pipe reactor on-line chromatograph detect butene-1 concentration and are respectively 8.5mol% and 8.2mol%.
Embodiment 4:
With embodiment 1, just the add-on of nucleator is 0.5 or 0.6 weight part, and first annular-pipe reactor and the second annular-pipe reactor on-line chromatograph detect butene-1 concentration and be respectively 13mol% and 11.5mol%.
Comparative Examples:
With embodiment 1, just change the butene-1 in first annular-pipe reactor and second annular-pipe reactor into ethene, the corresponding online chromatogram detects ethylene concentration and is respectively 2.8mol% and 2.5mol%, and the add-on of nucleator is 0.6 weight part.
Each embodiment resulting polymers analytical results and polymer physics performance are listed in table 1.
Table 1. embodiment polymers analysis results
| Butene-1 content mol% | NX8000 add-on weight part | Melting index g/10min | N-hexane extract g/100g | Modulus in flexure GPa | Mist degree % | HDT ℃ | |
| Testing standard | ?ASTMD1238 | GB/T5009.58 | ASTMD790 | ASTM1003 | ASTMD648 | ||
| Embodiment 1 | 5.0 | 0 | ?11.6 | Do not survey | 1.05 | 39.7 | 85.5 |
| 5.0 | 0.4 | ?12.2 | 1.4 | 1.20 | 7.13 | 80.8 | |
| 5.0 | 0.5 | ?12.0 | 1.4 | 1.22 | 6.38 | 76.3 | |
| 5.0 | 0.6 | ?11.5 | 1.4 | 1.18 | 5.54 | 78.0 | |
| Embodiment 2 | 1.8 | 0 | ?17.7 | Do not survey | 1.20 | 52.68 | 96.8 |
| 1.8 | 0.4 | ?18.3 | 0.8 | 1.57 | 11.11 | 98.1 | |
| 1.8 | 0.5 | ?19.0 | 0.8 | 1.56 | 7.6 | 96.8 | |
| 1.8 | 0.6 | ?22.2 | 0.8 | 1.56 | 7.36 | 95.2 | |
| Embodiment 3 | 2.8 | 0 | ?8.0 | Do not survey | 1.13 | 42.67 | 89.4 |
| 2.8 | 0.4 | ?9.9 | 1.0 | 1.33 | 8.35 | 86.8 | |
| 2.8 | 0.5 | ?9.0 | 1.0 | 1.32 | 6.7 | 86.6 | |
| 2.8 | 0.6 | ?10.5 | 1.0 | 1.32 | 6.51 | 86.4 | |
| Embodiment 4 | 4.0 | 0.5 | ?8.8 | 1.2 | 1.24 | 6.5 | 82.6 |
| 4.0 | 0.6 | ?9.0 | 1.2 | 1.25 | 6.0 | 81.5 | |
| Comparative Examples | Ethene 4.0 | 0.6 | ?9.6 | 2.2 | 1.10 | 6.8 | 76.0 |
By above data as can be seen, polypropene composition of the present invention is compared with traditional polypropene composition that contains ethylene-propylene random copolymer, n-hexane extract (promptly moving thing content) reduces greatly, and has high transparent, high rigidity and high heat resistance concurrently, is very suitable for food and pharmaceutical packing.
Claims (9)
1. polypropene composition includes the following component of blend: (A) propene-1-butene of butene-1 content 0.5～7.5mol%-1 random copolymers, 100 weight parts; (B) Millad NX8000 nucleator, 0.1～1 weight part.
2. polypropene composition as claimed in claim 1 is characterized in that: the butene-1 content of described propene-1-butene-1 random copolymers is 1～6mol%, preferred 1.5～5mol%.
3. polypropene composition as claimed in claim 1 is characterized in that: the consumption of described Millad NX8000 nucleator is 0.4～0.6 weight part, preferred 0.4～0.5 weight part.
4. polypropene composition as claimed in claim 1 is characterized in that: the melting index of 230 ℃/2.16kg of described composition is 0.5～50g/10min, preferred 3～30g/10min.
5. polypropene composition as claimed in claim 1 is characterized in that: the n-hexane extract of described composition is less than 1.5g/100g, and less than 12%, heat-drawn wire is greater than 75 ℃ through the 1mm of melt injection molding thick sheet mist degree, and modulus in flexure is greater than 1.1GPa.
6. polypropene composition as claimed in claim 5 is characterized in that: described n-hexane extract is less than 1.5g/100g, and less than 7%, heat-drawn wire is greater than 75 ℃ through the 1mm of melt injection molding thick sheet mist degree, and modulus in flexure is greater than 1.1GPa.
7. polypropene composition as claimed in claim 5 is characterized in that: described n-hexane extract is less than 1.2g/100g, and less than 7%, heat-drawn wire is greater than 85 ℃ through the 1mm of melt injection molding thick sheet mist degree, and modulus in flexure is greater than 1.3GPa.
8. polypropene composition as claimed in claim 5 is characterized in that: described n-hexane extract is less than 1.0g/100g, and less than 9%, heat-drawn wire is greater than 95 ℃ through the 1mm of melt injection molding thick sheet mist degree, and modulus in flexure is greater than 1.5GPa.
9. as the preparation method of each described polypropene composition among the claim 1-8, comprising: with described propene-1-butene-1 random copolymers powder with comprise that the auxiliary agent of described Millad NX8000 nucleator is by described weight proportion melt blending.
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| CN111100380A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polypropylene resin for hot-filling bottle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100098586A1 (en) * | 2008-10-21 | 2010-04-22 | Fina Technology, Inc. | Propylene Polymers for Lab/Medical Devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100098586A1 (en) * | 2008-10-21 | 2010-04-22 | Fina Technology, Inc. | Propylene Polymers for Lab/Medical Devices |
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|---|---|---|---|---|
| CN111100380A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polypropylene resin for hot-filling bottle |
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Application publication date: 20111109 |