CN1086394C - Catalyzer for ethylene polymerization and copolymerization and preparaing method thereof - Google Patents
Catalyzer for ethylene polymerization and copolymerization and preparaing method thereof Download PDFInfo
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- CN1086394C CN1086394C CN97121914A CN97121914A CN1086394C CN 1086394 C CN1086394 C CN 1086394C CN 97121914 A CN97121914 A CN 97121914A CN 97121914 A CN97121914 A CN 97121914A CN 1086394 C CN1086394 C CN 1086394C
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Abstract
The present invention relates to a catalyzer for ethylene polymerization or copolymerization, and a preparing method thereof. Active components of the catalyzer comprise a magnesium compound, fatty alcohol with 1 to 12 carbon atoms, at least one unsaturated fatty acid ester containing at least one hydroxy group, and (or) at least one reaction product of a water-in-oil type nonionic surface active agent, an organoaluminium compound and a titanium compound. The catalyzer has the advantages of simple preparing method and low cost. Polyethylene resin obtained after the catalyzer is used for the ethylene polymerization or the copolymerization has narrow particle size distribution and high apparent density.
Description
The present invention relates to a kind of Catalysts and its preparation method that is used for vinyl polymerization or copolymerization.
Since the seventies, it is the Ti-Mg high-effective carrier catalyst of carrier with the magnesium chloride that companies such as Mitsui petrochemical industry Co., Ltd. succeed in developing multiple, makes world's slurry process production polyolefin industry obtain development fast.More representational technology is the method for Mitsui oiling disclosed vinyl polymerization and copolymerization in Japanese Patent JP49-51378 (notification number JP50-32270), wherein being obtained by following substance reaction of catalyzer:
A, transition-metal catalyst component are by following component prepared in reaction:
(1) titanium or vanadium compound are selected from TiX
4, Ti (OR)
4-nX
n, VOX
3, VX
4, wherein X is a halogen, and R is an alkyl, and n is 0 or less than 4 integer,
(2) between-20 ℃～100 ℃, reaction product (a) and (b),
(a) Fatty Alcohol(C12-C14 and C12-C18) of magnesium dihalide and 1～12 carbon atom or aromatic alcohol reaction product between-l0 ℃～200 ℃, magnesium dihalide is 1: 0.1～10 with the mol ratio of alcohol,
(b) periodictable I main group is selected to the organometallic compound of III main group
RM wherein R is an alkyl or aryl, and M is lithium, sodium, polonium; RM ' wherein M ' is zinc, calcium; R
2-1MX
1Wherein X is a halogen, and l is 0 or 1; MAlR
4R '
3-mAlX
mWherein R ' is H or alkyl or aryl; R '
3-n(OR)
nR ' Al (OR) X;
B, periodictable I main group are selected from R to the organometallic compound of III main group "
3-mAlX
m, R '
3-n(OR)
n, R ' Al (OR) X, R
2-1MX
1
Wherein the mol ratio of titanium or vanadium and B component organometallic compound is 1: 1～10000 in the A component.
The concrete preparation method of this catalyzer is: magnesium dichloride through grinding in the lam-oil medium and ethanol synthesis generate MgCl
26C
2H
5OH alcohol adduct slurries are sloughed most of ethanol with aluminium diethyl monochloride generation esterification again, carry the titanium reaction with titanium tetrachloride at last, obtain Ti/MgCl
2High-effective carrier catalyst.This catalyst preparation process is simple, and reaction conditions is not harsh, processing ease, and activity is higher when being used for vinyl polymerization or copolymerization.But in whole catalyst preparation process, the irregular sheet form that has formed when the carrier magnesium chloride has kept former grinding substantially in the slurry reaction system causes the Ti/MgCl that finally obtains
2The solid catalyst particle shape is relatively poor, and thickness is inhomogeneous, and fine powder is more.In order to guarantee to obtain the catalyzer of better performances, to close the consumption of alcohol in the reaction be every mole of magnesium chloride more than at least four moles to lay special stress on alcohol in the specification sheets of this patent, especially with six moles for well, so the consumption of aluminum alkyls and titanium tetrachloride is all bigger.If pure consumption more after a little while, activity was lower when the catalyzer that obtains was used for vinyl polymerization, the relatively poor (polyvinyl apparent density≤0.3g/cm of particle shape
3), size-grade distribution is inhomogeneous, and (particle diameter greater than 900 μ coarse particlees and less than the fine particle of 78 μ all＞5wt%), because the particle shape of polymkeric substance is relatively poor, concentration of slurry during slurry polymerization is lower, directly influenced the raising of production equipment production efficiency, particularly fine powder is more, because the electrostatic effect exists bigger hidden danger.
For particle shape and the poly apparent density of raising of improving catalyzer, each company has developed a series of spheries and class spheric Ti/MgCl in succession
2Carried catalyst, most of patented technologies are that the magnesium dichloride alcohol adduct is formed homogeneous solution in high temperature (〉=110 ℃) system, with various liquid electronic donor compound capables and titanium compound reaction, cooperate proper technical conditions to make Ti/MgCl again
2Solid is spherical in shape or class is spherical separates out again.For example, Korea S Samsung General Chemicals Co., Ltd discloses the high activated catalyst that a kind of polyolefine is used in Chinese patent CN1099041A, it is that four 2-Ethylhexyl Alcohol things with magnesium dichloride are heated in decane and form the water white transparency homogeneous solution under 110 ℃ of high temperature, add electronic donor compound capable and titanium tetrachloride elder generation afterreactions such as propylene liquid acid 2-hydroxyl ethyl ester more successively, finally make Ti/MgCl
2Solid catalyst is spherolite shape separates out, and slurry polymerization obtains the polyvinyl resin apparent density and reaches 0.38～0.40 gram per centimeter
3, catalyst activity is 26～29 myriagrams polyethylene/gram titanium.JP55-135103 (US4315874) patented technology of Mitsui petrochemical complex Co., Ltd. be with magnesium dichloride five ethylates in kerosene, 120 ℃ of high temperature form homogeneous solution down, add tensio-active agent Emasol (the two stearates of sorbitan), under high-speed stirring, this pyrosol is injected in-10 ℃ the cold kerosene by a spray tube, the speed cold analysis goes out the spherical magnesium dichloride alcohol adduct carrier of 10～40 μ, with this ball type carrier successively with triethyl aluminum, ethyl benzoate and titanium tetrachloride reaction, finally obtain spherical Ti/MgCl
2High-effective carrier catalyst is used for the slurry process propylene polymerization.
Though above-mentioned patented technology has been improved the particle shape of carried catalyst to some extent and has been improved the polyolefinic apparent density of producing, it is complicated that but catalyst preparation process becomes, it must at first become the magnesium dichloride solid into even liquid magnesium compound by the alcohol mode of closing in high-temperature medium, in this homogeneous solution, use electronic donor compound capable or processing such as tensio-active agent and titanium tetrachloride, magnesium dichloride carrier particle spherical in shape is again separated out, and use the hydrocarbon solvent of high boiling point (〉=120 ℃) in the preparation process, make catalyst detergent, it is complicated more that dry and solvent recovery process becomes, and the catalyzer cost improves.
The objective of the invention is to overcome the defective that exists in the above-mentioned prior art, a kind of Catalysts and its preparation method that is used for vinyl polymerization or copolymerization is provided, this method for preparing catalyst is simple, cost is lower, and it is higher to be used for the polyvinyl resin narrower particle size distribution, the apparent density that obtain after vinyl polymerization or the copolymerization.
A kind of catalyzer that is used for vinyl polymerization or copolymerization of the present invention comprises following component:
A, transition-metal catalyst component, by following component prepared in reaction:
Between (1) 0 ℃～80 ℃, (a) and (b), (c) and reaction product (d),
(a) magnesium compound,
(b) Fatty Alcohol(C12-C14 and C12-C18) of 1～12 carbon atom, magnesium is 1: 0.1～10 with the mol ratio of alcohol,
(c) at least a unsaturated fatty acid ester and/or at least a oil bag that contains one or more hydroxyls
Water type nonionogenic tenside,
(d) organo-aluminium compound R '
3-mAlX
m, wherein X is a halogen, and R is an alkyl, and m is 0 or smaller or equal to 3
Integer,
(2) titanium compound Ti (OR)
4-nX
n, wherein X is a halogen, and R is an alkyl, and n is 0 or smaller or equal to 4 integer;
B, organo-aluminium compound R "
3-nAlX
n, wherein X is a halogen, and R ' is an alkyl, and n is 0 or less than 3 integer;
Among the above-mentioned component B among aluminium and the component A mol ratio of titanium be 20～250.
Magnesium compound comprises magnesium dichloride, dibrominated magnesium, two magnesium iodides among the catalyst component A of the present invention, and complex compound such as water of above magnesium dihalide, alcohol, one of them halogen atom is best by-oxyl or halo-oxyl institute metathetical derivative with the magnesium dichloride in the magnesium dihalide molecular formula in addition.
Fatty Alcohol(C12-C14 and C12-C18) comprises methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, is excellent with methyl alcohol and ethanol among the catalyst component A of the present invention; In every mole of magnesium compound, the consumption of alcohol is 1～6 mole, is the best with 3～4 moles.
Can add when the Fatty Alcohol(C12-C14 and C12-C18) of magnesium compound and 1～12 carbon atom reacts among the catalyst component A of the present invention aliphatic hydrocarbon as thinner as hexane, heptane, octane, decane, 1,2-ethylene dichloride and other hydro carbons or halogenated hydrocarbon compound; Consider that catalyst system of the present invention does not need to carry out under higher temperature, and be convenient to the recovery of thinner, preferably adopt hexane; The consumption of thinner is advisable to prepare suitable magnesium compound concentration of slurry, general every mole of magnesium compound meter, and the consumption of thinner is 1～5 liter, is preferably 2～3 liters.
(c) composition in the catalyst A component of the present invention---the unsaturated fatty acid ester that contains one or more hydroxyls can be selected a kind of in vinylformic acid 2-hydroxyl ethyl ester (HEA), methacrylic acid 2-hydroxyl ethyl ester (HEMA), vinylformic acid 2-hydroxypropyl acrylate (HPA), methacrylic acid 2-hydroxypropyl acrylate (HPMA), vinylformic acid 4-hydroxy butyl ester, the pentaerythritol triacrylate or their mixture for use; Its add-on is counted 0.01～0.5 mole with every mole of magnesium compound, is preferably 0.05～0.25 mole.
The above-mentioned unsaturated fatty acid ester that contains one or more hydroxyls is a kind of electron donor compound, its effect is the effect by hydroxyl and unsaturated link(age), magnesium compound and alcohol form in the alcohol adduct process its particle repaired or to swelling the alcohol adduct particle of magnesium compound carry out the particle shape reparation, make it be tending towards class sphere and homogenizing, to improve the particle form of final catalyzer.
(c) composition in the catalyst A component of the present invention---the water-in-oil-type nonionogenic tenside is selected polyhydric alcohol fatty acid ester class nonionogenic tenside or polyoxyethylene tensio-active agent for use, its HLB (hydrophile-lipophile balance value) value is advisable with 2～8, is preferably 3～6; Consumption is advisable with 0.1～1.0wt% of thinner, is preferably 0.4～0.8wt%.Wherein polyhydric alcohol fatty acid ester class nonionogenic tenside can be selected sucrose fatty ester (SE series) for use, sorbitan-fatty acid ester (Span series) is for example: sorbitan stearate, sorbitol anhydride oleate, sorbitan cetylate, the two stearates of glycerine, a kind of in the Zerol or their mixture; The polyoxyethylene tensio-active agent adopts alkylphenol polyoxyethylene;
Above-mentioned water-in-oil-type nonionogenic tenside, in inert diluent, by capillary effect, to swelling the alcohol adduct particle of magnesium compound carry out the particle shape reparation, make it be tending towards class sphere and homogenizing, to improve the particle form of final catalyzer.
Organo-aluminium compound R ' among the catalyst component A of the present invention
3-mAlX
m, can select a kind of in triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride and the sesquialter chloroethyl aluminium or their mixture for use, with aluminium diethyl monochloride the best; Its add-on is counted 1～4 mole with every mole of magnesium compound, is preferably 1.5～2.5 moles.
Titanium compound Ti (OR) among the catalyst component A of the present invention
4-nX
n, can select titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium for use, be best with the titanium tetrachloride; Its add-on is counted 1.0～6.0 moles with every mole of magnesium compound, is preferably 2.0～4.0 moles.
Organo-aluminium compound R among the catalyst component B of the present invention "
3-nAlX
n, can select triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride and sesquialter chloroethyl aluminium for use, be the best with triethyl aluminum and triisobutyl aluminium; Its add-on is 20～250 with the mol ratio of the titanium among aluminium among the component B and the component A, is preferably 50～150 moles.
The preparation method of catalyst component A of the present invention is:
(1) preparation of alcohol adduct slurries: under 0 ℃～80 ℃, in the aliphatic hydrocarbon thinner, the Fatty Alcohol(C12-C14 and C12-C18) of magnesium compound, 1～12 carbon atom, at least a unsaturated fatty acid ester and/or at least a water-in-oil-type nonionogenic tenside that contains one or more hydroxyls are mixed, obtain the alcohol adduct slurries of magnesium, after also can be earlier the Fatty Alcohol(C12-C14 and C12-C18) of magnesium compound and 1～12 carbon atom being formed the alcohol adduct slurries of magnesium, add at least a unsaturated fatty acid ester and/or at least a water-in-oil-type nonionogenic tenside that contains one or more hydroxyls again;
(2) alcohol adduct slurries and organo-aluminium compound are carried out esterification, temperature of reaction is 0 ℃～50 ℃;
(3) carboxylate slurries and titanium compound are carried the titanium reaction, temperature of reaction is 20 ℃～80 ℃;
(4),, obtain catalyst component A with solvent wash, drying with above-mentioned dope filtration.
The catalyzer that constitutes with catalyst component A of the present invention and component B is applicable to the equal polymerization of ethene and the copolymerization of ethene and other alpha-olefins, and polymerization methods can adopt slurry process, vapor phase process, solution method etc., wherein is best with the slurry process.Above-mentioned alpha-olefin can adopt propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.
Catalyzer of the present invention compared with prior art has with advantage:
(1) in Preparation of catalysts process of the present invention, use lower temperature (getting final product under the envrionment temperature) just can make magnesium halide and alcohol in thinner, form swollen alcohol adduct slurries, and need not at high temperature the magnesium halide dissolving be formed solution, also can obtain having the catalyzer of fine particle form, make that Preparation of catalysts technology is simple, easy to operate.
(2) consumption that lay special stress on alcohol closes in the reaction alcohol in the specification sheets of Japanese Patent JP49-51378 (notification number JP50-32270) is that every mole of magnesium chloride is more than at least four moles, especially with six moles for well, if when the consumption of alcohol was low, the particle form of catalyzer was bad; Catalyzer of the present invention has solved this problem by adding composition (c), relatively this point can be described very clearly from the data of table 1.(data of table 1 are to draw under identical condition, and unique difference is to have added composition (c) catalyzer of the present invention (example 4) raw material ratio in the example 4:
MgCl
2: EtOH: AlClEt
2: TiCl
4: HPMA=1: 4: 1.8: 2.7: 0.13 comparative example, 2 catalyzer raw materials ratio:
MgCl
2∶EtOH∶AlClEt
2∶TiCl
4＝1∶4∶1.8∶2.7
Table 1
| Examples Example 4 | (c) among the catalyst component A | Active ten thousand gPE/gTi | Apparent density g/cm 3 0.37 | Size distribution (wt%) | |||
| ＞900μ | 900～154μ | 154～78μ | ＜78μ | ||||
| HPMA | 83.5 | 4.5 | 75.4 | 19.6 | 0.4 | ||
| Compare 1 | / | 72.7 | 0.27 | 8.8 | 60.3 | 23.5 | 7.4 |
Find out from the data of table 1, use the poly apparent density of catalyzer gained of the present invention to be 0.37g/cm
3, wherein particle diameter be 78～900 μ account for 95%, and the apparent density of comparative example is 0.27g/cm
3, wherein particle diameter be 78～900 μ account for 83.8%.
(3) reduced pure consumption in the Preparation of catalysts process of the present invention, also reduced simultaneously the consumption of esterifying agent (organo-aluminium compound) and titanium compound, the consumption of composition is seldom and (c), price is also very cheap, therefore reduced the cost of catalyzer, simultaneously the aftertreatment technology of catalyzer has been more prone to.Catalyzer of the present invention (example 4) raw material ratio:
MgCl
2: EtOH: AlClEt
2: TiCl
4: HPMA=1: 4: 1.8: 2.7: the raw material ratio of 0.13 comparative example, 2 catalyzer:
MgCl
2: EtOH: AlClEt
2: TiCl
4=1: pure consumption has reduced by 33.3% in 6: 2.8: 4 catalyzer, the consumption of organoaluminum has lowered 28.6%, the consumption of titanium chloride has lowered 32.5%, therefore the cost of catalyzer has been lowered in the present invention widely, and the apparent density of resulting polymers is higher, size distribution narrower (seeing Table 2).
Table 2
| Embodiment | (c) among the catalyst component A | Active ten thousand gPE/gTi | Apparent density g/cm 3 0.37 | Size distribution (wt%) | |||
| ＞900μ | 900～154μ | 154～78μ | ＜78μ | ||||
| Example 4 | HPMA | 83.5 | 4.5 | 75.4 | 19.6 | 0.4 | |
| Compare 2 | / | 94.6 | 0.31 | 6.1 | 47.4 | 42.3 | 4.1 |
Embodiment
Example 1
1, the preparation of catalyst component A: under the nitrogen protection; in having the reaction flask of agitator, add 0.057 mole of anhydrous magnesium dichloride, 160 milliliters of hexanes of dehydration and sucrose fatty ester (SE-5 successively; HLB=5) 0.64 gram; be warming up to 50 ℃ under stirring; and under this temperature, stirred 30 minutes, obtain white slurries.After slurry temperature reduced to room temperature, drip 0.228 mole of dehydrated alcohol, being warming up to 30 ℃ of alcohol closes reaction and drips 0.103 mole of aluminium diethyl monochloride (being mixed with the hexane solution of 2.23 volumetric molar concentrations) after 2 hours, keep 35 ℃ of esterifications after 1.5 hours, be warming up to 60 ℃ and drip 0.154 mole of titanium tetrachloride, carry the titanium reaction after 2 hours, obtain pale yellow syrup.Filter out mother liquor, use hexane wash, obtain light yellow solid after the drying, wherein titaniferous 5.24wt%.
2, polymerization: in 2 liters stainless steel still, behind nitrogen replacement, in still, add 1.0 liters of hexanes of dehydration, triethyl aluminum 1.0 mmoles, above-mentioned catalyst component A (counting 0.0065 mole) successively with titanium, feed hydrogen to still after reactor is warming up to 70 ℃ and press 0.28MPa (gauge pressure), feed ethene to still again and press 0.75MPa (gauge pressure).At 80 ℃, polymerization is 2 hours under the 0.75MPa, obtains white polyethylene powder 207 grams, its polymerization activity is 66.5 myriagrams polyethylene/gram titanium, poly melting index is 0.621g/10min (testing method ASTM D-1238, following examples all with), and apparent density is 0.36 gram per centimeter
3(testing method ASTM D-1895-69, following examples all with).
Example 2
1, the preparation of catalyst component A: under the nitrogen protection; in having the reaction flask of agitator, add 0.051 mole of anhydrous magnesium dichloride, 150 milliliters of hexanes of dehydration and alkylphenol polyoxyethylene (NP-4 successively; HLB=5) 0.6 milliliter, stirred 30 minutes under the room temperature, obtain white slurries.Then, drip 0.206 mole of dehydrated alcohol, later operation steps is with example 1, and just the add-on of aluminium diethyl monochloride becomes 0.093 mole, and the add-on of titanium tetrachloride becomes 0.138 mole, obtains light yellow catalyst solid, wherein titaniferous 2.77wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 277.4 grams, its polymerization activity is 89.1 myriagrams polyethylene/gram titanium, and apparent density is 0.35 gram per centimeter
3
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 277.4 grams, its polymerization activity is 89.1 myriagrams polyethylene/gram titanium, and apparent density is 0.35 gram per centimeter
3
Example 3
1, the preparation of catalyst component A: under the nitrogen protection, in having the reaction flask of agitator, add 0.052 mole of anhydrous magnesium dichloride, 150 milliliters of dehydration hexanes successively, drip 0.208 mole of dehydrated alcohol under the room temperature, close reaction 1 hour at 30 ℃ of alcohol then, add vinylformic acid 2-hydroxyl ethyl ester (HEA) 6.5 mmoles again, be warming up to 40 ℃ of reactions 1 hour; Be cooled to 30 ℃ then, drip 0.094 mole of aluminium diethyl monochloride, be warming up to 35 ℃ of esterifications 1.5 hours; Be warming up to 60 ℃, drip 0.141 mole of titanium tetrachloride, carry titanium reaction 2 hours at 65 ℃; Filter out mother liquor, use hexane wash, obtain catalyst solid component A after the drying, wherein contain Ti=4.11wt%, HEA=3.42wt%, OC
2H
5=13.21wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 335.9 grams, its polymerization activity is 107.9 myriagrams polyethylene/gram titanium, and the polyethylene rerum natura sees Table 1.
Example 4
1, the preparation of catalyst component A: the preparation method is with example 3, only use methacrylic acid 2-hydroxypropyl acrylate (HPMA) 6.5 mmoles to replace vinylformic acid 2-hydroxyl ethyl ester (HEA) 6.5 mmoles, obtain catalyst solid component A, wherein contain Ti=3.65wt%, Mg=19.23 wt%, Cl=58.60 wt%, Al=0.35 wt%, HEA=5.77wt%, OC
2H
5=9.45wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 260 grams, its polymerization activity is 83.5 myriagrams polyethylene/gram titanium, and the polyethylene rerum natura sees Table 1.
Example 5
1, the preparation of catalyst component A: the preparation method is with example 4, and only the consumption with methacrylic acid 2-hydroxypropyl acrylate (HPMA) changes 5.2 mmoles into by 6.5 mmoles, obtains catalyst solid component A, wherein contains Ti=4.18wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 207 grams, its polymerization activity is 66.5 myriagrams polyethylene/gram titanium, and the polyethylene rerum natura sees Table 1.
Example 6
1, the preparation of catalyst component A: the preparation method is with example 4, and only the consumption with methacrylic acid 2-hydroxypropyl acrylate (HPMA) changes 3.4 mmoles into by 6.5 mmoles, obtains catalyst solid component A, wherein contains Ti=4.91wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 235 grams, its polymerization activity is 75.3 myriagrams polyethylene/gram titanium, and the polyethylene rerum natura sees Table 1.
Comparative example 1:
1, the preparation of catalyst component A: change into 2 hours except that not using methacrylic acid 2-hydroxypropyl acrylate and alcohol to close the reaction times, all the other preparation methods obtain catalyst solid component A with example 4, wherein contain Ti=4.62wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 226.4 grams, its polymerization activity is 72.7 myriagrams polyethylene/gram titanium, and the polyethylene rerum natura sees Table 1.
Comparative example 2:
1, the preparation of catalyst component A: the preparation method is with comparative example 1, only feeding quantity is changed into 0.052 mole of anhydrous magnesium dichloride, 0.312 mole of dehydrated alcohol, 0.146 mole of aluminium diethyl monochloride, 0.208 mole of titanium tetrachloride, obtain catalyst solid component A, wherein contain Ti=5.25wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 294.5 grams, its polymerization activity is 94.6 myriagrams polyethylene/gram titanium, and the polyethylene rerum natura sees Table 1.
Example 7
1, the preparation of catalyst component A: under the nitrogen protection, in having the reaction flask of agitator, add 175 milliliters of 0.061 mole of anhydrous magnesium dichlorides, SE-5 0.62 gram, dehydration hexane successively, be warming up to 50 ℃, stir and reduce to room temperature after 30 minutes, drip 0.244 mole of dehydrated alcohol, close reaction 1 hour at 30 ℃ of alcohol then, add 0.75 milliliter of vinylformic acid 2-hydroxyl ethyl ester (HEA) again, be warming up to 40 ℃ of reactions 1 hour; Be cooled to 30 ℃ then, drip 0.110 mole of aluminium diethyl monochloride, be warming up to 35 ℃ of esterifications 1.5 hours; Be warming up to 60 ℃, drip 0.165 mole of titanium tetrachloride, carry titanium reaction 2 hours at 65 ℃; Filter out mother liquor, use hexane wash, obtain catalyst solid component A after the drying, wherein contain Ti=2.99wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 233.8 grams, its polymerization activity is 78.2 myriagrams polyethylene/gram titanium, and the polyethylene rerum natura sees Table 1.
Example 8
1, the preparation of catalyst component A: under the nitrogen protection, in having the reaction flask of agitator, add 0.054 mole of anhydrous magnesium dichloride, 0.6 milliliter of NP-4,150 milliliters of dehydration hexanes successively, stir under the room temperature and drip 0.215 mole of dehydrated alcohol after 30 minutes, close reaction 1 hour at 30 ℃ of alcohol then, add methacrylic acid 2-hydroxypropyl acrylate (HPMA) 5.4 mmoles again, be warming up to 40 ℃ of reactions 1 hour; Be cooled to 30 ℃ then, drip 0.097 mole of aluminium diethyl monochloride, be warming up to 35 ℃ of esterifications 1.5 hours; Be warming up to 60 ℃, drip 0.145 mole of titanium tetrachloride, carry titanium reaction 2 hours at 65 ℃: filter out mother liquor, use hexane wash, obtain catalyst solid component A after the drying, wherein contain Ti=2.87wt%.
2, polymerization: use the catalyst component of above-mentioned preparation, polymerization process is with example 1.Obtain white polyethylene powder 198.6 grams, its polymerization activity is 69.2 myriagrams polyethylene/gram titanium, and the polyethylene rerum natura sees Table 3.
Table 3
| Embodiment | (b) among the catalyst component A | Active ten thousand gPE/gTi | Melting index g/10min | Apparent density g/cm 3 | Size distribution (wt%) | |||
| ＞900μ | 900～154μ | 154～78μ | ＜78μ | |||||
| Example 1 | SE-5 | 66.5 | 0.621 | 0.36 | ||||
| Example 2 | NP-4 | 89.1 | 0.573 | 0.35 | ||||
| Example 3 | HEA | 107.9 | 0.359 | 0.35 | 4.0 | 69.0 | 25.0 | 2.0 |
| Example 4 | HPMA | 83.5 | 0.364 | 0.37 | 4.5 | 75.4 | 19.6 | 0.4 |
| Example 5 | HPMA | 66.5 | 0.665 | 0.35 | 6.2 | 63.6 | 27.8 | 2.4 |
| Example 6 | HPMA | 75.3 | 0.860 | 0.32 | 0.6 | 87.0 | 11.1 | 1.4 |
| Example 7 | SE-5+HEA | 78.2 | 0.572 | 0.35 | 0.8 | 56.1 | 41.8 | 1.3 |
| Example 8 | NP-4+HPMA | 69.2 | 0.534 | 0.36 | 6.5 | 47.3 | 41.0 | 3.2 |
| Compare 1 | / | 72.7 | 0.367 | 0.27 | 8.8 | 60.3 | 23.5 | 7.4 |
| Compare 2 | / | 94.6 | 0.402 | 0.31 | 6.1 | 47.4 | 42.3 | 4.1 |
Example 9
In 2 liters stainless steel still, behind nitrogen replacement, the catalyst component A (counting 0.0065 mole) that in still, adds 1.0 liters of hexanes of dehydration, triethyl aluminum 1.0 mmoles successively, makes by example 4 with titanium, feed hydrogen to still after reactor is warming up to 60 ℃ and press 0.2MPa (gauge pressure), gas mixture (containing butene-1 6.0mol%) to the still that feeds ethene and butene-1 is again pressed 0.7MPa (gauge pressure).At 70 ℃, polymerization is 2 hours under the 0.7MPa, obtains copolymer powder 137 grams of polyethylene and butene-1, and its polymerization activity is 44 myriagrams polymkeric substance/gram titanium, and the density of ethylene copolymer is 0.9388g/cm
3, the degree of branching is 5.5CH
3/ 1000C, melting index is 0.404g/10min.
Example 10～13
Polymerization: the catalyst component of use-case 4, polymerization process be with example 1, but hydrogen add-on when changing polymerization, and the add-on of ethene obtains the polyethylene of different molecular weight, the results are shown in Table 4.
Table 4
| Embodiment | Hydrogen add-on (MPa) | Ethene add-on (MPa) | Catalyst activity (ten thousand gPE/gTi) | Melting index (g/10min) |
| Example 10 | 0.15 | 0.60 | 130.5 | 0.051 |
| Example 11 | 0.28 | 0.47 | 83.5 | 0.364 |
| Example 12 | 0.40 | 0.35 | 35.6 | 26.0 |
| Example 13 | 0.60 | 0.15 | 6.2 | 236.3 |
Claims (13)
1, a kind of catalyzer that is used for vinyl polymerization or copolymerization comprises following component:
A, transition-metal catalyst component, by following component prepared in reaction:
Between (1) 0 ℃～80 ℃, (a) and (b), (c) and reaction product (d),
(a) magnesium compound,
(b) Fatty Alcohol(C12-C14 and C12-C18) of 1～12 carbon atom, magnesium is 1: 0.1～10 with the mol ratio of alcohol,
(c) at least a unsaturated fatty acid ester and/or at least a oil bag that contains one or more hydroxyls
Water type nonionogenic tenside,
(d) organo-aluminium compound R '
3-mAlX
m, wherein X is a halogen, and R is an alkyl, and m is 0 or smaller or equal to 3
Integer,
(2) titanium compound Ti (OR)
4-nX
n, wherein X is a halogen, and R is an alkyl, and n is 0 or smaller or equal to 4 integer;
B, organo-aluminium compound R "
3-nAlX
n, wherein X is a halogen, and R ' is an alkyl, and n is 0 or less than 3 integer;
Among the above-mentioned component B among aluminium and the component A mol ratio of titanium be 20～250.
2, catalyzer according to claim 1, it is characterized in that, magnesium compound described in the catalyst component A is selected from a kind of by in-oxyl or the halo-oxyl institute metathetical derivative of one of them halogen atom in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and the magnesium dihalide molecular formula, or their mixture.
3, catalyzer according to claim 1 is characterized in that, the Fatty Alcohol(C12-C14 and C12-C18) described in the catalyst component A is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, the octanol or their mixture.
4, catalyzer according to claim 1 is characterized in that, the mol ratio of Fatty Alcohol(C12-C14 and C12-C18) described in the catalyst component A and magnesium compound is 3～4.
5, catalyzer according to claim 1, it is characterized in that, the unsaturated fatty acid ester that contains one or more hydroxyls described in the catalyst component A is selected a kind of of vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, vinylformic acid 4-hydroxy butyl ester, pentaerythritol triacrylate for use, or their mixture.
6, catalyzer according to claim 1 is characterized in that, the add-on of the unsaturated fatty acid ester that contains one or more hydroxyls described in the catalyst component A is counted 0.01～0.5 mole with every mole of magnesium compound.
7, catalyzer according to claim 1 is characterized in that, the water-in-oil-type nonionogenic tenside described in the catalyst component A is selected polyhydric alcohol fatty acid ester class nonionogenic tenside or polyoxyethylene tensio-active agent for use, and its HLB value is 2～6.
8, catalyzer according to claim 1 is characterized in that, the add-on of the water-in-oil-type nonionogenic tenside described in the catalyst component A is that benchmark is 0.1～1.0wt% with the weight of thinner.
9, catalyzer according to claim 7, it is characterized in that described polyhydric alcohol fatty acid ester class nonionogenic tenside is selected a kind of in the two stearates of sucrose stearate, sorbitan stearate, sorbitol anhydride oleate, sorbitan cetylate, glycerine, the Zerol or their mixture for use.
10, catalyzer according to claim 7 is characterized in that, described polyoxyethylene tensio-active agent adopts alkylphenol polyoxyethylene.
11, catalyzer according to claim 1, it is characterized in that, organo-aluminium compound described in the catalyst component A is selected a kind of in triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride and the sesquialter chloroethyl aluminium or their mixture for use.
12, catalyzer according to claim 1, it is characterized in that, titanium compound described in the catalyst component A is selected a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium or their mixture for use.
13, the preparation method of component A is in the described catalyzer of one of claim 1～12:
(1) preparation of alcohol adduct slurries: under 0 ℃～80 ℃, in the aliphatic hydrocarbon thinner, the Fatty Alcohol(C12-C14 and C12-C18) of magnesium compound, 1～12 carbon atom, at least a unsaturated fatty acid ester and/or at least a water-in-oil-type nonionogenic tenside that contains one or more hydroxyls are mixed, obtain the alcohol adduct slurries of magnesium, after also can be earlier the Fatty Alcohol(C12-C14 and C12-C18) of magnesium compound and 1～12 carbon atom being formed the alcohol adduct slurries of magnesium, add at least a unsaturated fatty acid ester and/or at least a water-in-oil-type nonionogenic tenside that contains one or more hydroxyls again;
(2) alcohol adduct slurries and organo-aluminium compound are carried out esterification;
(3) carboxylate slurries and titanium compound are carried the titanium reaction;
(4),, obtain catalyst component A with solvent wash, drying with above-mentioned dope filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121914A CN1086394C (en) | 1997-11-18 | 1997-11-18 | Catalyzer for ethylene polymerization and copolymerization and preparaing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121914A CN1086394C (en) | 1997-11-18 | 1997-11-18 | Catalyzer for ethylene polymerization and copolymerization and preparaing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1180712A CN1180712A (en) | 1998-05-06 |
| CN1086394C true CN1086394C (en) | 2002-06-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97121914A Expired - Lifetime CN1086394C (en) | 1997-11-18 | 1997-11-18 | Catalyzer for ethylene polymerization and copolymerization and preparaing method thereof |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096474C (en) * | 1998-12-30 | 2002-12-18 | 化学工业部北京化工研究院 | Composite catalyst for synthesizing polyethylene or ethylene copolymer with wide molecular weight distribution and its preparation and application |
| CN101684165B (en) * | 2008-09-28 | 2012-04-18 | 中国石油化工股份有限公司 | Magnesium halide adduct and preparation method and application thereof |
| CN101864013B (en) * | 2010-06-24 | 2013-04-24 | 东北石油大学 | Catalyst for gas-phase polymerization or copolymerization of ethylene and preparation method thereof |
| CN104031184B (en) * | 2013-03-06 | 2016-05-11 | 中国石油天然气股份有限公司 | The solid titanium catalyst of a kind of vinyl polymerization or combined polymerization and preparation thereof and application |
| US9714302B2 (en) | 2014-10-10 | 2017-07-25 | W. R. Grace & Co.—Conn. | Process for preparing spherical polymerization catalyst components for use in olefin polymerizations |
| CN108219040B (en) * | 2018-01-09 | 2020-07-17 | 为信（深圳）材料科技有限公司 | Components, preparation method and application of spherical alkoxy magnesium particles |
| CN108409896B (en) * | 2018-04-04 | 2021-02-05 | 朴蓝聚烯烃科技发展（上海）有限公司 | Ziegler-natta catalyst compositions and uses thereof |
| CN113087824B (en) * | 2021-03-19 | 2023-02-10 | 上海簇睿低碳能源技术有限公司 | Improved Ziegler-Natta catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315874A (en) * | 1979-04-11 | 1982-02-16 | Mitsui Petrochemical Industries Ltd. | Process for the production of spherical carrier particles for olefin polymerization catalysts |
| CN1099041A (en) * | 1993-05-07 | 1995-02-22 | 三星综合化学株式会社 | Highly active catalyst for polymerization of olefins and method for the preparation of the same |
-
1997
- 1997-11-18 CN CN97121914A patent/CN1086394C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315874A (en) * | 1979-04-11 | 1982-02-16 | Mitsui Petrochemical Industries Ltd. | Process for the production of spherical carrier particles for olefin polymerization catalysts |
| CN1099041A (en) * | 1993-05-07 | 1995-02-22 | 三星综合化学株式会社 | Highly active catalyst for polymerization of olefins and method for the preparation of the same |
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| Publication number | Publication date |
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| CN1180712A (en) | 1998-05-06 |
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