CN1115349C - Process for preparing stable polyolefine - Google Patents
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- CN1115349C CN1115349C CN 98101246 CN98101246A CN1115349C CN 1115349 C CN1115349 C CN 1115349C CN 98101246 CN98101246 CN 98101246 CN 98101246 A CN98101246 A CN 98101246A CN 1115349 C CN1115349 C CN 1115349C
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Abstract
The present invention relates to a process for preparing stable polyolefine. Magnesium chloride loaded with a titanium compound and an ester and ether internal donor compound is used as a solid catalyst. Alpha-olefin monomers are polymerized by an aluminum alkyl cocatalyst and a phenolic antioxidant, wherein the solid catalyst comprises 15 to 25 wt% of magnesium, 1.0 to 5.0 wt% of titanium and 8.0 to 15.0 wt% of internal donor compound; a weight ratio of ether to ester is from 0.6 to 2.8. The polyolefine prepared by the process has good oxidation resistance.
Description
The present invention is a kind of preparation method of stabilization of polyolefins product, specifically, is a kind of method that extruding pelletization can be produced stabilization of polymer that need not.
In the prior art, generally to stablize the method for olefin polymer be after polymerization polymkeric substance to be mixed with stablizer in the preparation of Cai Yonging, extruding pelletization then, thus obtain stable polyolefin products.Owing in the mixing process stablizer is evenly distributed in polymkeric substance, so stabilising effect is bad.
Recently, directly in polymerization process, add stablizer rapidly, thereby the agglomeration technique of exempting from that obtains stablizing olefin product is developed.Its advantage is the stabilization polyolefin products that makes, but need not through the extruding pelletization process just long-term storage, transport and carry out the post-treatment processing.Used stablizer mainly comprises oxidation inhibitor, photostabilizer and thermo-stabilizer in the preparation, also can add other additive, on spherical Ziegler-Natta catalyst, add hindered amine and three phosphides as CN1039606A during polymerization at alkene, preparation can also add phenol type oxidation inhibitor to the polymkeric substance of heat and oxidatively stable.The antioxidant property of the polymkeric substance that this method adding hindered amine and phosphatide obtain is bad, adds phenol type antioxidant and can make the polymkeric substance variable color, and the less stable of this polymkeric substance is described.
CN1102652A discloses a kind of method of stablizing alpha-olefin for preparing, be applicable to two or three still tandem process processes, this method is being carried in the presence of titanium catalyst and the aluminum alkyl catalyst, in first polymeric kettle, add a kind of stablizer so that the nascent polymer kernel is stable earlier, and then add stablizer of the same race or not of the same race in the second or the 3rd still, so that the mesectoderm of polymkeric substance is stable.Used stablizer is selected from phenolic antioxidant, the phosphorous acid ester of band aryl, phosphoric acid ester aid anti-oxidants, thioether type thermal stabilizing agent, hindered amine light stabilizer, metal passivator and halogen-absorber.Though this method can obtain stability polyolefin products preferably, its preparation method is comparatively loaded down with trivial details, and application is restricted.
CN1051915A then discloses a kind of with particulate polyolefin product method of stabilizing, this method will prepare spherical polyolefin products with the method for routine, handle with a kind of molten mixture of stablizer that comprises, stablizer is deposited on forms stable coating on the polyolefin products, thereby obtain stable polyolefin products.The used polyolefinic molten mixture of processing of this method comprises and accounts for the following multiple stablizer of polymer weight percentage ratio: A) be the organophosphite of liquid or their mixture under one or more room temperatures of 0.02%～0.15%, B) one or more fusing points of 0.25%～0.2% are 45～130 ℃ phenolic antioxidant, also can add following component, C) one or more thioethers or organic polysulfide, D) one or more hindered amine as light stabilizer, E) one or more are selected from and are the paraffinic of liquid and cycloalkane under the room temperature, the thinner of epoxy soybean oil or Toenol 1140 and silicone oil and alkene oligomer.When handling polymer beads, answer the separated and catalyzer of selective polymer to take off after the stage alive with this method.
CN1074222A also discloses a kind of method for preparing the stabilization of polyolefins product, it is catalyzer that this method adopts the magnesium chloride solids component that is loaded with ethers electron donor compound and titanium compound, when polymerization, add aluminum alkyl catalyst and one or more phenol stabilizers, can obtain stable polyolefin products.Should contain one or more spaces hindered phenol group in the used phenolic antioxidant structural formula.Use this method only to add the stabilization polypropylene that phenolic antioxidant makes when polymerization, the oxidation induction time under 180 ℃ is the longest only to be 39 minutes.
The objective of the invention is on the basis of above-mentioned prior art, a kind of method that phenolic antioxidant prepares the stabilization of polyolefins product that adds in polymerization process is provided.
It is solid catalyst that method of the present invention adopts the active magnesium chloride that is loaded with titanium compound and ether and ester class internal electron donor compound, in the presence of aluminum alkyl catalyst and phenolic antioxidant, makes olefinic monomer carry out polymerization, makes the stabilization of polyolefins product.Wherein Mg content is 15～25 heavy % in the solid catalyst, titanium content is the heavy % in 1.O～5.0, and the internal electron donor compounds content is 8～15 heavy %, and the internal electron donor compound is for having the ester of general formula (I) and the ether of general formula (II), the weight ratio of ether and ester is 0.6～2.8
In formula (I) and the formula (II), R
1～R
4Be selected from C
1～C
10Alkyl, aryl or aralkyl, R
1～R
4Can be identical, also can be different.
Two ester compounds in the described formula (I) are preferably o-benzene butyl phthalate ester.
In the described formula (II) 1,3-diether compound, preferred R wherein
3, R
4Be methyl, R
1, R
2Can be identical or different, be selected from the ether of sec.-propyl, isobutyl-, the tertiary butyl, cyclohexyl, isopentyl, cyclohexyl ethyl, as 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal; 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, most preferably 2,2-diisobutyl-1,3-Propanal dimethyl acetal.
Described titanium compound is selected from halogenated titanium, titan-alkoxide or halogenated alcoholate, as, titanous chloride, titanium tetrachloride, four titanium butoxide, be preferably titanium tetrachloride.
The used active magnesium chloride ball type carrier of solid catalyst of the present invention makes with the described method of CN1109067A.The alcohol amount of containing in this carrier is 1.5～4.0, be preferably 2.0～3.0 moles/mole MgCl
2, its preparation process is as follows:
(1) alcohol closes reaction: the mixture with methyl-silicone oil and whiteruss is a medium, and magnesium chloride and ethanol were reacted 2～4 hours at 110～130 ℃ according to the amount of 2.0～3.0 milliliters of ethanol/gram magnesium chloride.
(2) disperse adducts: alcohol is closed reactant transfer in the mixture medium that is preheated to 110～130 ℃, is made up of methyl-silicone oil and whiteruss, the medium volume is 1.2～2.0 times of alcohol adduct volume, stirs 3～6 minutes with 1500～3000 rev/mins rotating speeds.
(3) chilling solidifies: the adduct emulsion after will disperseing is transferred in advance and is chilled in-15～-30 ℃ the inert solvent medium, and the volume ratio of medium and emulsion is 2～2.5, stirs 20～30 minutes.
(4) Separation and Recovery: treat that above-mentioned mixed system temperature rises to the room temperature after-filtration naturally and goes out solids, the liquid (volume) by 1～1.5 solid (weight) is than wash 3 times vacuum or 50～60 ℃ of nitrogen dryings with inert solvent.
The preparation method of used solid catalyst is as follows:
(1) by the amount of 3.0～6.0 milliliters in every gram carrier the magnesium chloride ball type carrier is mixed with inert solvent, gained suspension is pressed Ti/Mg mol ratio 30～60, preferably 35～45 ratio adds in the compound titanium solution that is chilled to 0～-10 ℃ in advance, slowly be warming up to 60～80 ℃, press magnesium/ether mol ratio 8～22, the ratio of magnesium/ester mol ratio 8～15 adds the ester of formula (I) and the ether of formula (II), and the mol ratio of ether and ester is 0.4～1.70.100～125 ℃ were reacted 1.5～4 hours, and filtered while hot is isolated solid particulate.
(2) ratio according to Ti/Mg mol ratio 20～50 is added to solid particulate in the compound titanium solution of preheating, stirs and 100～125 ℃ of reactions 1～2 hour, filtered while hot was isolated solid particulate.
(3) with free Cl on 50～70 ℃ the inert solvent flush away particle
-, vacuum or 50～60 ℃ of nitrogen dryings.
Described inert solvent is selected from hexane, heptane, octane, nonane, decane, gasoline.
During polyreaction, the promotor that is used with solid catalyst is selected from alkylaluminium cpd, and preferred three hexyl aluminium or triisobutyl aluminium or the mixture of the two, its consumption are aluminium/titanium mol ratio 100～1500.
The used phenolic antioxidant of the present invention is selected from phenolic compound commonly used in the prior art, generally speaking, should comprise one or more space hindered phenol groups with following structure in the phenolic compound structural formula,
R in the formula is selected from-CHR
2Or-the OR group, R in the formula or the R base among the R ' can be identical or different, are selected from hydrogen, C
1～C
30Alkyl.C
3～C
30Cycloalkyl, C
6～C
30Aryl, C
7～C
30Aralkyl or alkaryl, perhaps C
1～C
30Alkoxyl group; Described one or more R base can at random contain a plurality of functional groups, especially piperidyl or-COOR " ,-O-,-S-,-NHR " or-OR " etc. functional group, R in the described functional group " be selected from hydrogen, C
1～C
30Alkyl, C
3～C
30Cycloalkyl, C
6～C
30Aryl, C
7～C
30Aralkyl or alkaryl, in the solemnity-OH group adjacent R has one at least for hydrogen.
The exemplary of above-mentioned oxidation inhibitor has: 2,6-di-t-butyl-4-sylvan, 2,6-di-t-butyl-4-ethyl phenol, the 2-tertiary butyl-4,6-two-octadecyl phenol, 2,6-di-t-butyl-4-n-Hexadecane oxygen base phenol, 4,4 '-thiobis (the 6-tertiary butyl-2-butyl-2-sylvan), four [methylene radical (3,5-di-tert-butyl-hydroxy phenyl propionic ester)] methane, four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, preferred oxidation inhibitor are that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, its trade names are antioxidant 1010 (Irganox-1010).
Present method is applicable to that monomer is CH
2The polymerization process of the alpha-olefin of=CHR, with production stable polymer or multipolymer, R is C in the formula
3～C
10Alkyl.During polymerization, phenolic antioxidant adds during polyreaction or before the polyreaction.
Under the batchwise polymerization situation, phenolic antioxidant can during the polyreaction before ingredient of solid catalyst adds or join in the reactor together or thereafter.
Under the successive polymerization situation, phenolic antioxidant can add reactor or adding respectively with solid catalyst.If use the serial reaction device, it can be added in arbitrary reactor.Also can be when polyreaction stop, catalyzer is added before the deactivation.
Except that adding phenolic antioxidant, also can add other known stablizers, as the steady agent of hindered amine light (HALS), organophosphite etc.
Described hindered amine as light stabilizer, the steady agent of preferred polymeric type hindered amine light, its add-on is 0.01～0.9 gram photostabilizer/100 gram polymkeric substance, is preferably 0.05～0.5 gram/100 gram polymkeric substance.The add-on of other all kinds of stablizers is generally 0.01～0.9 gram/100 gram polymkeric substance, is preferably 0.05～0.5 gram/100 gram polymkeric substance.
The adding of phenolic antioxidant and other stablizer can be with pure or with the aliphatic series or the aromatic hydrocarbon of hexane, heptane, hexanaphthene and toluene, or lower alcohol or acetone is that the solution form of solvent preparation adds, and can also liquid monomer alkene be the solvent adding.
For obtaining higher degree of isotacticity product, can add the external electron donor compound during polymerization, it is R that the external electron donor compound is selected from general formula
1R
2Si (OR)
2Silicon compound, R wherein
1, R
2Be selected from C with R
1～C
10Alkyl, C
3～C
30Cycloalkyl, C
6～C
30Aryl, C
7～C
30Aralkyl or alkaryl, preferred silicon compound is dimethoxydiphenylsilane or cyclohexyl methyl dimethoxy silane, the consumption of silane is an Al/Si mol ratio 30～40 with respect to the promotor aluminum alkyls.
The stabilization of polyolefins product that makes with the present invention has higher resistance of oxidation, and as reaching 65 minutes with the polypropylene of present method preparation oxidation induction time 180 ℃ the time is the longest, and other performances of polymkeric substance are not affected.In addition, used solid catalyst among the present invention and is that the catalyzer of internal electron donor is compared with two ethers separately, and the consumption of diether significantly reduces, and has reduced the cost of catalyzer.
Describe the present invention in detail below by embodiment, but the present invention is not limited to this.
Example 1
This example carries out the propylene polymerization experiment under the situation that does not add oxidation inhibitor.
(1) method according to CN1109067A prepares ball type carrier.
With 34 gram anhydrous magnesium dichlorides (Fushun Aluminium Works's Industrial products); (Beijing Chemical Plant produces 80 milliliters of dehydrated alcohols; analytical pure) and 100 milliliters of methyl-silicone oils (chemical industry two factories in Beijing produce; chemical pure; viscosity is 300 centipoises); the 100 milliliters of liquid paraffin (chemical plant of seeking talent, Beijing; chemical pure; viscosity is 40 centipoises) under nitrogen protection, join in 500 milliliters of reaction flasks that agitator and prolong are housed; be heated to 120 ℃; react to the magnesium dichloride solid and dissolve fully; shift this solution while hot to methyl-silicone oil and each mixed solution of 150 milliliters of whiteruss; stirred 4 minutes with 2000～3000 rev/mins speed; put into and give in the anhydrous hexane (Beijing Yanshan Petrochemical Company, technical grade) that is chilled to-30 ℃, be stirred to system temperature and rise to room temperature; filter; the gained solid is with 200 milliliters of anhydrous hexane 3 times, and vacuum-drying obtains ball type carrier.
(2) Preparation of catalysts
Under nitrogen protection; the above-mentioned carrier of 6.2 grams is suspended in a small amount of anhydrous hexane; add 120 milliliters then and be chilled to (connection chemical plant chemical reagent work in Beijing in-10 ℃ the titanium tetrachloride solution in advance; technical grade); stir down and slowly heat up, under 80 ℃, add 0.7 milliliter 2 respectively; 2-diisobutyl-1, the 3-Propanal dimethyl acetal (is pressed EP0361493A
1Method synthetic) and 0.52 milliliter of diisobutyl phthalate (Beijing chemical reagent work, analytical pure), be warming up to 110 ℃ and reacted 2 hours, filter, solid particulate is put into 50 milliliters of titanium tetrachlorides, 120 ℃ were reacted 1 hour, filter, solid with anhydrous hexane to there not being Cl
-Exist, make catalyzer, its Ti content is 2.76 heavy %, Ti content metric measurement.
(3) mass polymerization
Under nitrogen atmosphere, in 5 liters of polymeric kettles, add 5.3 milliliters of the triethyl aluminums of 37.2 milligrams of above-mentioned catalyzer, 0.8M, continue to add propylene gas then, polymerization is 2 hours under 70 ℃, 3.0MPa, obtain 766 gram polymkeric substance, productive rate is 20.6 a kilograms/gram catalyzer, and degree of isotacticity is 95%.Utilizing differential scanning (DSC) to record the polyacrylic oxidation induction time of product at 180 ℃ is 11.65 minutes.Press the method for CNS GB1843-80, GB9341-88 and GB1040-79, measure the polyacrylic mechanical property of gained, the results are shown in Table 1 with INSTRON-1122 tensile testing machine, CSI-137 shock-testing machine.
Example 2
This example carries out propylene polymerization experiment adding under the situation of oxidation inhibitor.
Under nitrogen protection; 32.7 milliliters of the catalyzer of adding example 1 preparation in 5 liters of polymeric kettles, 4.7 milliliters of the triethyl aluminums of 0.8M, anti-oxidant Irganox-1,010 0.27 gram; feed propylene gas then; at 70 ℃, polymerization is 2 hours under the 3.0MPa pressure, gets polymkeric substance 664 grams; productive rate is 20.3 a kilograms/gram catalyzer; degree of isotacticity is 94.5%, 180 ℃ of following oxidation induction time 49.32 minutes, and other mechanical property of polymkeric substance sees Table 1.
Example 3
Carry out the propylene polymerization experiment by the method for example 2, the add-on of different is catalyzer is 34.2 milligrams, the add-on of triethyl aluminum is that 4.9 milliliters, the add-on of anti-oxidant Irganox-1010 are 0.49 gram, behind the pressure polymerization 2 hours, obtain 714 gram polymkeric substance, productive rate is 20.9 a kilograms/gram catalyzer, and the polymkeric substance degree of isotacticity is 95%, 180 ℃ of following oxidation induction times are 63.58 minutes, and other mechanical property sees Table 1.
Example 4
This example carries out the propylene polymerization experiment in the presence of oxidation inhibitor and the steady agent of hindered amine light.
Under nitrogen protection; 36.5 milliliters of the catalyzer that adding example 1 makes in 5 liters of polymeric kettles, 5.1 milliliters of the triethyl aluminums of 0.8M, anti-oxidant Irganox-1,010 0.28 gram; steady agent Irgafos-944 0.4 gram of light; feed propylene gas then, at 70 ℃, polymerization is 2 hours under the 3.0MPa pressure; obtain 715 gram polymkeric substance; productive rate is 20.1 a kilograms/gram catalyzer, and the polymkeric substance degree of isotacticity is 94.0%, 180 ℃ of following oxidation induction time 55.82 minutes.
Table 1
| Example 1 | Example 2 | Example 3 | Example 4 | ||
| Solid catalyst, milligram | 37.2 | 32.7 | 34.2 | 35.6 | |
| Three hexyl aluminium (0.8M), milliliter | 5.3 | 4.7 | 4.9 | 5.1 | |
| Anti-oxidant Irganox-1010, gram | 0.27 | 0.49 | 0.28 | ||
| The steady agent of light, gram | 0.4 | ||||
| Productive rate, kg of polymer/gram catalyzer | 20.6 | 20.3 | 20.9 | 20.1 | |
| Polymkeric substance | Degree of isotacticity, % | 95.0 | 94.5 | 95.0 | 94.0 |
| Oxidation induction time (180 ℃) divides | 11.65 | 49.32 | 65.38 | 55.82 | |
| Yield strength, MPa | 29.52 | 30.30 | 31.61 | ||
| Flexural strength, MPa | 23.01 | 23.65 | |||
| Modulus in flexure, MPa | 953.4 | 1038.6 | 1048.6 | ||
| Shock strength, Jiao Er/rice | 36.6 | 37.8 | 41.9 | ||
Claims (9)
1, a kind of method for preparing stabilization of polyolefins, it is characterized in that the magnesium chloride to be loaded with halogenated titanium or titan-alkoxide and ester and ether internal electron donor compound is a solid catalyst, in the presence of aluminum alkyl catalyst and phenolic antioxidant, make olefinic monomer carry out polymerization, wherein Mg content is 15～25 heavy % in the solid catalyst, titanium content is 1.0～5.0 heavy %, the internal electron donor compounds content is 8.0～15.0 heavy %, the internal electron donor compound is for to have the ester of general formula (I) and the ether of general formula (II), and the weight ratio of ether and ester is 0.6～2.8
Among formula (I), (II), R
1～R
4Be selected from C
1～C
10Alkyl, aryl or aralkyl, they can be identical or different.
2, in accordance with the method for claim 1, it is characterized in that halogenated titanium is selected from titanium tetrachloride, titan-alkoxide is selected from four titanium butoxide.
3, in accordance with the method for claim 1, the ester that it is characterized in that formula (I) is a diisobutyl phthalate, and the ether of formula (II) is 2,2-diisobutyl-1,3-Propanal dimethyl acetal.
Can add also when 4, in accordance with the method for claim 1, it is characterized in that the olefinic monomer polymerization that to be selected from general formula be R
1R
2Si (OR)
2The external electron donor compound, its consumption is an Al/Si mol ratio 30～40 with respect to the promotor aluminum alkyls.
5, in accordance with the method for claim 1, it is characterized in that described phenolic antioxidant, comprise one or more space hindered phenol groups in its structure with following structure:
R ' is selected from-CHR in the formula
2Or-the OR group, R in the formula or the R base among the R ' can be identical or different, be selected from hydrogen, C
1～C
30Alkyl, C
3～C
30Cycloalkyl, C
6～C
30Aryl, C
7～C
30Aralkyl or alkaryl, or C
1～C
30Alkoxyl group; Described one or more R can at random contain a plurality of functional groups, these functional groups be selected from piperidyl or-COOR " ,-O-,-S-,-NHR " or-OR ", wherein R " is selected from hydrogen, C
1～C
30Alkyl, C
3～C
30Cycloalkyl, C
6～C
30Aryl, C
7～C
30Alkaryl or aralkyl, but should satisfy-OH adjacent R has at least one not to be hydrogen.
6, in accordance with the method for claim 5, it is characterized in that phenolic antioxidant is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
7, according to claim 1,6, any method of 7, the add-on that it is characterized in that phenolic antioxidant is 0.01～0.9 gram/100 gram polymkeric substance.
8, in accordance with the method for claim 1, also can add hindered amine as light stabilizer when it is characterized in that polymerization, its add-on is 0.01～0.9 gram photostabilizer/100 gram polymkeric substance.
9, in accordance with the method for claim 1, it is characterized in that described olefinic monomer is for having CH
2The alpha-olefin of=CHR structure, R wherein are C
3～C
10Alkyl.
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| CN 98101246 CN1115349C (en) | 1998-04-03 | 1998-04-03 | Process for preparing stable polyolefine |
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|---|---|---|---|
| CN 98101246 CN1115349C (en) | 1998-04-03 | 1998-04-03 | Process for preparing stable polyolefine |
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| CN104193857B (en) * | 2007-12-21 | 2017-05-24 | 格雷斯公司 | Self-limiting catalyst composition with bidentate internal donor |
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