CN1057846A - Process for catalytic synthesis - Google Patents
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- CN1057846A CN1057846A CN 90103217 CN90103217A CN1057846A CN 1057846 A CN1057846 A CN 1057846A CN 90103217 CN90103217 CN 90103217 CN 90103217 A CN90103217 A CN 90103217A CN 1057846 A CN1057846 A CN 1057846A
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Abstract
The activity of improved catalysts and performance, for alpha-olefine polymerizing or copolymerization, it is characterized by: the middle reaction of resultant of reaction (a) that adds hydrogenation polysiloxane and organo-magnesium compound with at least a organic diacid compound and ester compound thereof, (1) makes the halogen compound reaction direct and titanium of above-mentioned resultant of reaction generate solid (A) again, or (2) shilling its with mixture (b) reaction of at least a alcohols and organo-aluminium compound, again with the halogen compound reaction generation solid (A) of titanium; And be combined with the catalyzer composition that machine aluminium compound (B) is constituted, with the method for alpha-olefine polymerizing or copolymerization.
Description
The present invention system is about the alpha-olefine polymerizing that adopts novel high activated catalyst or the method for copolymerization, sees mellow and fullly outside its product, and granularity is concentrated, and for industrial easy to operate, carries easily.
Because the activity of catalyzer is high,, concentrate because of particle diameter again so can omit the step of deliming, superfine little powder amount is few, and centrifugal and dry operation can be finished smoothly, does not have the anxiety of fine powder blocking pipeline, mellow and full because of outward appearance again, therefore can lower the resistance of pipeline conveying, make processing ease.
The present invention system is with reaction in the resultant of reaction (a) of at least a organic diacid compound and ester compound adding hydrogenation polysiloxane and organo-magnesium compound, again
(1) make the halogen compound reaction direct and titanium of above-mentioned resultant of reaction generate solid (A), or
(2) shilling itself and mixture (b) reaction of at least a alcohols and organo-aluminium compound are again with the halogen compound reaction generation solid (A) of titanium;
And be combined with the catalyzer composition that machine aluminium compound (B) is constituted, with the method for alpha-olefine polymerizing or copolymerization.
The present invention's characteristic is as follows:
(1) active high, thus the step of deactivation and deliming can be omitted,
(2) for hydrogen equimolecular quantity conditioning agent sensitivity, the molecular weight of controlling polymers easily,
(3) growing amount of paraffin is few,
(4) be fit to the two-section type converging operation, cooperate the copolymerization of ethene and alpha-olefin, adjust molecular weight distribution, make the requirement of the suitable various product processibilities of polymkeric substance,
(5) diameter of particle is concentrated, and outward appearance is mellow and full, and fine powder amount is few, carries easily.
The organic diacid compound that the catalyzer composition is used among the present invention means the organic diacid compound (I) with following ordinary construction formula:
R wherein
1Be H
2Or the divalent organic base of 1～20 carbon number, as :=CHC
4H
9,=CH
2,=C
6H
4Deng, example has: Fu acid, propanedioic acid, butyl malonic acid, oxalic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dibromo-succinic acid, pyrovinic acid, maleic acid, FUMARIC ACID TECH GRADE, methylfumaric acid, methylene-succinic acid, 3-oxygen pentanedioic acid, 2-amino (generation)-1,4-Succinic Acid, 2 aminopentanedioic acid Si Qing Fu acid, Si Lv Fu acid, Er Lv Fu acid, m-phthalic acid, terephthalic acid, hydroxy-butanedioic acid, dyhydrobutanedioic acid, mesoxalic acid, chloric acid etc.
Above-mentioned again organic diacid compound (I) also comprises that its anhydrous compound promptly has the organic acid anhydride compound (II) of following ordinary construction formula:
R wherein
1Be H
2Or the divalent organic base of 1～20 carbon number, as :=CHC
4H
9,=CH
2,=C
6H
4Deng, example has: Fu acid anhydride, propane dianhydride, butyl propane dianhydride, second dianhydride, succinic anhydride, own dianhydride, glutaric anhydride, laurylene base succinic anhydride, MALEIC ANHYDRIDE MIN 99.5,2-chlorine MALEIC ANHYDRIDE MIN 99.5, propylene succinic anhydride, methyl succinic anhydride, methylene radical succinic anhydride etc.
The organic diacid ester cpds that the catalyzer composition is used among the present invention means the organic diacid ester cpds (III) with following ordinary construction formula:
R wherein
1Be H
2Or the divalent organic base of 1～20 carbon number, as :=CHC
4H
9,=CH
2,=C
6H
4Deng; R
2It is any monovalent organic radical of 1～12 carbon number.Example has: Fu dimethyl phthalate ， diethyl phthalate ， Fu acid di-n-propyl ester Fu acid diisopropyl ester ， Fu acid di-n-butyl ， Fu acid diisobutyl ester Fu acid two n-pentyl ester ， Fu acid two just own Zhi ， Fu dioctyl phthalates, dimethyl malonate, diethyl malonate, Diisopropyl malonate, the propanedioic acid di-n-butyl, propanedioic acid dihexyl, propanedioic acid dioctyl ester, the butyl malonic acid dimethyl ester, the butyl malonic acid diethyl ester, butyl malonic acid dipropyl, butyl malonic acid dibutylester, ethylene dimethyl, diethyl oxalate, Ethanedioic acid, dipropyl ester, ethylene sebacate, dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, the Succinic Acid dihexyl, Methyl glutarate, ethyl glutarate, pentanedioic acid dipropyl, the pentanedioic acid dibutylester, the pentanedioic acid dihexyl, dimethyl adipate, diethylene adipate, dipropyl adipate, Polycizer W 260, dihexyl adipate, suberic acid dimethyl ester, the suberic acid dipropyl, the suberic acid diethyl ester, suberic acid dibutylester, pyrovinic acid dimethyl ester, the pyrovinic acid diethyl ester, the pyrovinic acid dipropyl, pyrovinic acid dibutylester, pyrovinic acid dihexyl, the pyrovinic acid dioctyl ester, dimethyl isophthalate, dimethyl isophthalate, m-phthalic acid dibutylester, dimethyl terephthalate (DMT), diethyl terephthalate etc.
The hydrogenation polysiloxane that the catalyzer composition is used among the present invention means the silicoorganic compound (IV) with following tectonic element:
R wherein
3For being selected from alkyl, aryl, aralkyl, alkoxyl group, any monovalent organic radicals such as aryloxy; A=0,1,2; B=1,2,3; A+b≤3, compound or its mixture with any polymerization degree, its viscosity is the following persons of 1000 Duo in the time of 25 ℃, the structure of its end end base then can be arbitrarily not active group such as trialkylsilanyl in addition the blockader also can.Specific examples is as tetramethyl disiloxane, phenylbenzene sily oxide, trimethylammonium cyclotrisiloxane, tetramethyl-ring tetrasiloxane, hydrogenated methyl polysiloxane, phenyl hydrogenation polysiloxane, oxyethyl group hydrogenation polysiloxane, ring octyl group hydrogenation polysiloxane, chloro-phenyl-hydrogenation polysiloxane etc.
The organo-magnesium compound that the catalyzer composition is used among the present invention means the organo-magnesium compound (V) with following constitutional formula:
R wherein
4Be alkyl; X is a halogen atom; M, n are between 0～1, and m+n=1.If m=0 wherein, n=1 then refers to the jesse greener reagent (R of general narrow sense
4MgX); If m=1, n=0.Then be alkyl magnesium (MgR
4 2); Still have in addition with the represented various organomagnesium halides of (V) formula and with the ligand of ethers.Specific examples is as methylmagnesium-chloride, ethylmagnesium chloride, n-propyl chlorination magnesium, ethylmagnesium bromide, normal-butyl chlorination magnesium, tertiary butyl chlorination magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, diphenyl magnesium, dioctyl magnesium, phenyl-magnesium-chloride, ethyl-normal-butyl magnesium etc.
Silicoorganic compound (IV) are as follows with the method for organo-magnesium compound (V) reaction solution body (a): under inert gas atmosphere, in the synthetic organo-magnesium compound of appropriate solvent, drip silicoorganic compound one by one, continue to stir again after adding for some time make react completely after, promptly get liquid (a).
Reaction is carried out under-50 ℃～100 ℃ usually, is preferably in room temperature～80 ℃, and the time then is 30 minutes～300 minutes.
Solvent in the reaction can be selected the unreactive hydrocarbons series solvent for use, for example: hexane, heptane, hexanaphthene, benzene, toluene, dimethylbenzene etc., aforementioned organo-magnesium compound then uses the solvent of ether series, as diethyl ether, dibutyl ether, tetrahydrofuran (THF) etc.
The adding proportion of silicoorganic compound and organo-magnesium compound in the raw material is generally with Si-O: Mg-R
4Be good at=1: 0.05～1.
When aforementioned organo-magnesium compound is solvent with the ethers, can make final solid catalyst (A) that bad character is arranged,, and remove the method for ethers, can use the distillation mode so generally the inert organic solvents that must add than ethers boiling point height replaces it.
Organic diacid compound (I) and organic acid anhydride compound (II) and organic diacid ester cpds (III) can carry out under-50～100 ℃ with the reaction of the resultant of reaction (a) of above-mentioned silicoorganic compound and organo-magnesium compound, reaction times is several minutes～100 minutes, and the ratio of interpolation is R
1(COOH)
2Or R
1(CO)
2O or R
1(COOR
2)
2: MgR
4=1: 1～50; Organic diacid and ester compound thereof (I), (II), (III) are if solid compounds then makes it be dissolved in fully in the liquid (a), and restir reacts for some time.
Add the organic diacid compound and can make active the raising, and polymerisate powder bulk specific weight is big, outward appearance is mellow and full, if do not add this type of organic diacid compound, though still have characteristics of high reactivity, the product powder morphology is poor, fine powder amount is many, is unfavorable for the centrifugal of processing procedure, operations such as drying.
Add the organic diacid ester cpds particle diameter is increased, and polymerisate powder outward appearance is mellow and full.
Use simultaneously if mix organic diacid compounds and ester compound thereof, then can doublely obtain the advantage of two kinds of compounds: can make active the raising, and polymerisate powder outward appearance is mellow and full, bulk specific weight also can improve, and particle diameter increases, and fine powder amount is few.
The titanium halogen compound that the catalyzer composition is used among the present invention means the titanium halogen compound (VI) with following ordinary construction formula:
R wherein
5For taking from any monovalent organic radical of 1～8 carbon number; X is a halogen atom; N=1～4, specific examples has: titanium tetrachloride, titanium tetrabromide, oxyethyl group titanous chloride, butoxy titanous chloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, dibutoxy titanium dichloride etc.
The alcohol compound that the catalyzer composition is used among the present invention means the alcohol compound (VII) with following ordinary construction formula:
R wherein
6For taking from any monovalent organic radical of 1～20 carbon number; Carbochain then be straight or branched all can, also can mix two or more alcohols and participate in reaction.Specific examples has: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol, 2-ethyl-1-hexanol, n-dodecanol etc.
The organo-aluminium compound that use mixes with alcohols among the present invention means the organo-aluminium compound (VIII) with following ordinary construction formula:
R wherein
7For taking from any monovalent organic radical of 1～8 carbon number; X is a halogen atom, hydrogen atom or alkoxyl group; 3＞n＞0.Specific examples has: diethyl aluminum chloride, dibutyl aluminum chloride, ADEH, dibutyl aluminum hydride, diethyl aluminum ethylate, ethylalumlinium sesquichloride etc.
The mixture of alcohols and organo-aluminium compound (b) ties up under 0～150 ℃ and reacts among the present invention, and the reaction times is 30 minutes to 300 minutes, and R wherein
6OH:Al-R
7=0.1～10: 1, the alcohols of selection and organo-aluminium compound have more than and are limited to a kind ofly, can respectively select more than one to mix use mutually.Reaction needed is carried out in the inertia aromatic hydrocarbon solvent, benzene for example, toluene, chlorobenzene etc.
After aforementioned organic diacid (ester) compound and organosilicon and organo-magnesium compound resultant of reaction (a) contact reacts, if again with the mixture (b) of above-mentioned alcohols and organo-aluminium compound when contacting, then being reflected at 0～150 ℃ carries out, 30 minutes～300 minutes reaction times, and Al wherein: Mg=0.1～20: 1.
The reaction of the reaction of titanium halogen compound and aforementioned liquids (a) and organic diacid (ester) compound resultant of reaction or titanium fontanel compound and aforementioned liquids (a) and organic diacid (ester) compound and alcohols and organoaluminum mixture (b) resultant of reaction must be carried out at-30～150 ℃, be preferably in 0～100 ℃, 30 minutes～300 minutes reaction times, and Ti: Mg=1～20: 1 wherein, reaction is preferably in the inertia aromatic hydrocarbon solvent to be carried out, benzene for example, toluene, chlorobenzene etc., the good and homogeneous of product granularity of acquisition, if adopt alkane solvent, as hexane, heptane etc. are though still can keep the characteristics of high reactivity, but size-grade distribution difference and bulk specific weight are very low, are unfavorable for operation.
Above-mentioned reaction ends, and extracts supernatant liquid out partly, solid with the free titanium halogen compound of inert organic solvents wash residual after, promptly obtain solid catalyst (A), the alkane that can use is washed solvent and is comprised: hexane, heptane, lam-oil etc.The temperature that alkane is washed is carried out under room temperature～70 ℃, be washed till solvent layer colourless till.If it is clean that free titanium halogen compound does not give, then active the reduction, and the paraffin of lower molecular weight increases.
With the solid catalyst (A) that the aforesaid method allotment forms, wherein every gram solid contains titanium atom 1～10%(weight fraction).
The organo-aluminium compound (B) that catalyzer second composition is used among the present invention means the organo-aluminium compound (IX) with following ordinary construction formula:
R wherein
8For taking from any monovalent organic radical of 1～8 carbon number; X is a halogen atom, hydrogen atom or alkoxyl group; N=1～3, specific examples has: trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, ADEH, dibutyl aluminum hydride, diethyl aluminum ethylate, ethylalumlinium sesquichloride etc.
Catalyzer composition among the present invention is to contact the back former with organo-aluminium compound (B) with above-mentioned solid catalyst (A), need only stir under the inert gas atmosphere to get final product in container, and ratio wherein is: Ti: Al=1: 1～1000 grammeatom ratio.
The polymerization of alpha-olefin or copolymerization among the present invention, its condition is identical with general Ziegler-Natta type catalyzer, all can carry out in liquid phase or gas phase, also can use the above reactive mode of continuous second order.Be that this catalyzer composition is scattered among the inert organic solvents during liquid phase, as hexane, heptane, lam-oil etc. are sent into alpha-olefin in the reactive tank and can be carried out polyreaction, and temperature is good with 30 ℃～200 ℃, be preferably in 60 ℃～100 ℃, pressure is normal pressure～50Kg/cm
2, can use hydrogen equimolecular quantity conditioning agent, account for 1～80% of reaction total pressure.The add-on of organo-aluminium compound in the polymerization (B) is good to contain aluminium 0.1～50 mmole in every liter of solvent, is preferably in 0.3～10 mmole.
The adjusting of molecular weight can be used hydrogen, changes temperature, and methods such as catalyzer usage quantity are wherein the most effective with hydrogen again.
The present invention's catalyzer can close for vinyl polymerization or ethene and alpha-olefin copolymer, and alpha-olefin wherein is as propylene, 1-butylene, and the 1-hexene, the 1-octene, 4-methyl-1-pentene etc., the alpha-olefin add-on during copolymerization is 0～10% weight fraction.
Following examples describe the present invention in detail, but non-limiting the present invention's technical scope.
(analytical procedure)
Mi
2: melting index, ASTM D1238,190 ℃, 2.16Kg, the g/10 of unit minute.
Embodiment 1
1. the modulation of resultant of reaction (a):
In inner thorough drying and glass reactor with nitrogen replacement, getting the tetrahydrofuran solution 50 milliliters (being equivalent to 90 milli despatches that magnesium) and 34 milliliters the toluene of normal-butyl chlorination magnesium inserts wherein, stir 5.9 milliliters of the hydrogenated methyl polysiloxane that splash into the trimethicone blockade down slowly (25 ℃ time viscosity be 30 centistokes) (being equivalent to silicon-oxygen 99 mmoles), this reaction is thermopositive reaction, so the palpus cooling, dripping off the back reacted 1 hour down at 70 ℃, be cooled to room temperature, add 50 milliliters toluene.Remove 90 milliliters of the mixed solvents of tetrahydrofuran (THF) and toluene in 160 mmhg and 50 ℃ of following underpressure distillation, redistillation is once under identical conditions to add 90 milliliters toluene, the liquid of gained gets the liquid (a) of magnesium density [Mg] 1.33 mol with dilution with toluene.
2. the modulation of solid catalyst composition (A):
In inner thorough drying and glass reactor with nitrogen replacement, getting 50 milliliters of above-mentioned resultant of reaction liquid (a) and toluene inserts wherein for 83 milliliters, with the microbalance Cheng Qu Fu of precision acid 1.254 Ke Ji diethyl phthalate 1.29 grams, add in the above-mentioned solution, stir and be heated to 50 ℃ of ， Zhi Fu acid and dissolve also homodisperse fully.
Insert 40 milliliters titanium tetrachloride in dropping funnel, splash into slowly in the stirring in the above-mentioned mixing liquid, keep 50 ℃ and drip off, sustained reaction is 2 hours again.
With the free composition several of normal hexane solvent flush away, till the clarification of upper strata solvent, get solid catalyst composition (A) under the normal temperature, wherein every gram solid contains 85 milligrams of titanium atoms.
3. the polymerization of ethene:
Has agitator, in 2 liters of stainless steel pressure stills of heating and cooling apparatus, inner thorough drying and complete with nitrogen replacement, insert 800 milliliters normal hexane, after being warming up to 60 ℃, add 4 milligrams of triethyl aluminum 1.0 mmoles and above-mentioned solid catalyst compositions (A) in regular turn, then import hydrogen 2.5Kg/cm
2, be warming up to 85 ℃ and import continuously ethene and make and keep total head 8Kg/cm
2Gauge pressure, sustained reaction are after 1 hour, and pressure release is cooled off, and filters and drying solid.
Get white polyethylene powder 180 grams, catalyst efficiency 45Kg/g catalyzer, Mi
23.3, bulk specific weight 0.275g/ml, median size 280 μ, product powder amount (＜74 μ) has 0.42%.
Comparative example 1
2. the modulation of solid catalyst composition (A):
Solid catalyst composition (A) concocting method as embodiment 1 does not react but do not make with Fu acid, directly titanium tetrachloride is splashed in the liquid composition (a).Get solid catalyst composition (A), wherein every gram solid contains 70 milligrams of titanium atoms.
3. the polymerization of ethene:
Polymerizing condition 3. as embodiment 1
Get white polyethylene powder 125 grams, catalyst efficiency 31Kg/g catalyzer, Mi
22.9, bulk specific weight 0.231g/ml, median size 150 μ, product powder amount (＜74 μ) has 5.5%.
Comparative example 2
2. the modulation of solid catalyst composition (A):
As solid catalyst composition (A) concocting method of embodiment 1, react but only make with Fu acid 1.254 grams, get solid catalyst composition (A), wherein every gram solid contains 85 milligrams of titanium atoms.
3. the polymerization of ethene:
Polymerizing condition 3. as embodiment 1
Get white polyethylene powder 175 grams, catalyst efficiency 44Kg/g catalyzer, Mi
22.7, bulk specific weight 0.265g/ml, median size 170 μ, product powder amount (＜74 μ) has 0.6%.
Embodiment 2-8
2. the modulation of solid catalyst composition (A):
As solid catalyst composition (A) concocting method of embodiment 1, but shown in the schedule of proportion 1 of the organic diacid of use and ester class thereof.
3. the polymerization of ethene:
As the solid catalyst composition (A) of table 1 and the polymerizing condition of embodiment 1, polymerisate character is detailed lists in the table 2.
Comparative example 3-5
2. the modulation of solid catalyst composition (A):
As solid catalyst composition (A) concocting method of embodiment 1, but the ratio of the organic diacid of use and ester class thereof is as shown in table 1.
3. the polymerization of ethene:
As the solid catalyst composition (A) of table 1 and the polymerizing condition of embodiment 1, polymerisate character is detailed lists in the table 2.
Embodiment 9-18
2. the modulation of solid catalyst composition (A):
As solid catalyst composition (A) concocting method of embodiment 1, but the ratio of the organic diacid of use and ester class thereof is as shown in table 3.
3. the polymerization of ethene:
As the solid catalyst composition (A) of table 3 and the polymerizing condition of embodiment 1, polymerisate character is detailed lists in the table 4.
Embodiment 20
3. the copolymerization of ethene and 1-butylene:
In the commercially available pressure gas cylinder of perfect vacuum drying, charge into 1-butylene to pressure 0.5Kg/cm
2, charge into ethene again to stagnation pressure 25Kg/cm
2Standby.
As solid catalyst composition (A) concocting method and the polymerizing condition of embodiment 1, but the ethene that continuous importing is ready in advance, 1-butylene mixed gas, total head 8Kg/cm
2After the gauge pressure sustained reaction 1 hour, pressure release, cooling is filtered and drying solid.
Get white polyethylene powder 195 grams, catalyst efficiency 48.8Kg/g catalyzer, Mi
22.5, bulk specific weight 0.265g/ml, median size 285 μ, product powder amount 0.44%, density 0.9570g/cm
3
Embodiment 21-28
3. the copolymerization of ethene and 1-butylene:
As the solid catalyst composition (A) of table 5 and the copolymerization condition of embodiment 20, ethene and 1-butylene blending ratio and polymerisate character are detailed lists in the table 5.
Table 1
The catalyzer allotment
Organic diacid (gram) organic diacid ester (gram) titanium content weight %
Embodiment-
1 Fu acid, 1.254 diethyl phthalates 1.290 8.5
2 " acid 0.880 " diethyl phthalate 0.905 8.4
3 " acid 0.880 " diethyl phthalate 1.290 7.9
4 " acid 1.254 " diethyl phthalate 0.905 8.2
5 " acid 1.730 " diethyl phthalate 0.905 8.3
6 " acid 2.412 " diethyl phthalate 0.905 8.5
7 " acid 0.880 " diethyl phthalate 1.240 8.1
8 " acid 1.254 " diethyl phthalate 1.240 8.2
Comparative example-
1??-??-??7.0
2 Fu acid 1.254-8.5
3 " acid 2.412-8.5
4-diethyl phthalate 1.290 8.7
5-" diethyl phthalate 2.504 7.9
Table 2
Polyreaction
The active Mi of output
2Bulk specific weight is average＜74 μ % remarks
(gram) Kg/g g/ g/ml particle diameter μ
Catalyzer 10 minutes
Embodiment-
1 180 45.0 3.3 0.275 280 0.42 powder outward appearances are mellow and full
2 190 47.5 3.2 0.295 265 0.40 powder outward appearances are mellow and full
3 173 43.3 3.1 0.271 280 0.40 powder outward appearances are mellow and full
4 175 43.8 3.1 0.280 260 0.45 powder outward appearances are mellow and full
5 152 38.0 3.0 0.277 265 0.50 powder outward appearances are mellow and full
6 125 31.3 2.7 0.263 270 0.50 powder outward appearances are mellow and full
7 168 42.0 3.1 0.262 250 0.50 powder outward appearances are mellow and full
8 157 39.3 2.8 0.251 255 0.45 powder outward appearances are mellow and full
Comparative example-
1??125??31.3??2.9??0.231??150??5.50
2??175??43.8??2.7??0.265??170??0.60
3 120 30.0 2.2 0.252 175 0.40 powder outward appearances are mellow and full
4 120 30.0 3.0 0.225 290 0.40 powder outward appearances are mellow and full
5 107 26.8 2.9 0.210 300 0.30 powder outward appearances are mellow and full
Table 3
The catalyzer allotment
Organic diacid (gram) organic diacid ester (gram) titanium content
Weight %
Embodiment-
9 propanedioic acid, 0.544 diethyl phthalate 0.905 8.0
10 propanedioic acid 0.544 " dibutyl phthalate 1.240 8.3
11 propanedioic acid, 0.544 propanedioic acid di-n-butyl 0.860 7.8
12 Fu acid anhydrides, 0.832 diethyl phthalate 0.905 7.9
13 " acid anhydride 0.832 Diisopropyl malonate 0.775 8.4
14 " sour 0.880 propanedioic acid di-n-butyl 0.860 7.9
15 oxalic acids, 0.459 diethyl phthalate 0.905 8.1
16 oxalic acids, 0.459 propanedioic acid di-n-butyl 0.860 8.2
17 terephthalic acids, 0.880 diethyl phthalate 0.905 8.2
18 terephthalic acids, 0.880 Diisopropyl malonate 0.775 8.4
Table 4
Polyreaction
The active Mi of output
2Bulk specific weight is average＜74 μ % remarks
(gram) Kg/g g/ g/ml particle diameter μ
Catalyzer 10 minutes
Embodiment-
9 155 38.8 3.5 0.279 250 0.52 powder outward appearances are mellow and full
10 140 35.0 4.0 0.288 255 0.50 powder outward appearances are mellow and full
11 139 34.8 3.3 0.286 260 0.46 powder outward appearances are mellow and full
12 155 38.8 2.9 0.291 280 0.48 powder outward appearances are mellow and full
13 160 40.0 3.8 0.284 255 0.48 powder outward appearances are mellow and full
14 154 38.5 3.5 0.276 270 0.52 powder outward appearances are mellow and full
15 148 37.0 3.5 0.269 290 0.60 powder outward appearances are mellow and full
16 137 34.3 4.1 0.277 285 0.49 powder outward appearances are mellow and full
17 156 39.0 2.9 0.275 260 0.56 powder outward appearances are mellow and full
18 153 38.3 2.8 0.290 270 0.55 powder outward appearances are mellow and full
Table 5
Copolymerization
The active Mi of catalyzer 1-butylene output
2Bulk specific weight density
Composition (A) branch rate %(gram) Kg/g g/ g/ml g/cm
3
Catalyzer 10 minutes
Embodiment-
20 embodiment 1 3.9 195 48.8 2.5 0.265 0.9570
21 embodiment 1 5.8 194 48.5 2.1 0.256 0.9525
22 embodiment 1 7.7 188 47.0 1.5 0.241 0.9480
23 embodiment 2 3.9 195 48.8 3.0 0.281 0.9560
24 embodiment 2 5.8 190 47.5 2.5 0.276 0.9520
25 embodiment 2 7.7 188 47.0 2.0 0.269 0.9475
26 embodiment 9 3.9 160 40.0 3.6 0.264 0.9550
27 embodiment 9 5.8 163 40.8 2.9 0.255 0.9510
28 embodiment 9 7.7 157 39.3 2.2 0.245 0.9465
Claims (9)
1, a kind of synthetic method that supplies the high activated catalyst of vinyl polymerization or copolymerization is characterized by:
The middle reaction of resultant of reaction (a) that adds hydrogenation polysiloxane and organo-magnesium compound with at least a organic diacid compound or its ester compound generates (b), again
(1) make above-mentioned resultant of reaction (b) directly with the halogen compound reaction generation solid (A) of titanium or
(2) shilling (b) generates (d) with mixture (c) reaction of at least a alcohols and organo-aluminium compound, and the halogen compound reaction with titanium generates solid (A) again;
And be combined with the catalyzer that machine aluminium compound (B) is constituted,
Synthetic method:
Organic diacid compound wherein means the organic acid anhydride compound that organic diacid compound with following ordinary construction formula I or anhydrous compound promptly have following ordinary construction formula II:
R
1Be H
2Or the divalent organic base of 1～20 carbon number.
Organic diacid ester cpds wherein means that the ester derivative of above-mentioned organic diacid compound (I) promptly has the organic diacid ester cpds of following ordinary construction formula III:
R
2Be H
2Or the divalent organic base of 1～20 carbon number, R
2Be any monovalent organic radical of 1～12 carbon number,
Hydrogenation polysiloxane wherein means the silicoorganic compound with following tectonic element (IV):
R
3For being selected from alkyl, aryl, aralkyl, alkoxyl group, any monovalent organic radicals such as aryloxy;
A=0,1,2; B=1,2,3; A+b＜3, compound or its mixture with any polymerization degree, its viscosity is the following persons of 1000 Duo in the time of 25 ℃.
Organo-magnesium compound wherein means the organo-magnesium compound with following constitutional formula (V):
R
4Be alkyl; X is a halogen atom; M, n are between 0～1, and m+n=1,
Resultant of reaction wherein (a) is that hydrogenation polysiloxane compound (IV) is got with organo-magnesium compound (V) contact reacts, is reflected at and carries out under-50 ℃～100 ℃ 30 minutes～300 minutes, wherein the ratio Si-O of silicon compound and magnesium compound: Mg-R
4=1: 0.05～1 mol ratio.
Resultant of reaction wherein (b) is that organic diacid compound (I) or organic acid anhydride compound (II) or organic diacid ester cpds (III) etc. are got with resultant of reaction (a) contact reacts, be reflected at and carried out under-50～100 ℃ several minutes～100 minutes, wherein organic diacid compound (I) or organic acid anhydride compound (II) or organic diacid ester cpds (III) are R with the ratio of resultant of reaction (a)
1(COOH)
2Or R
1(CO)
2O or R
1(COOR
2)
2: Mg=1: 1～50,
Titanium halogen compound wherein means the titanium halogen compound with following ordinary construction formula IV:
R
5For taking from any monovalent organic radical of 1～8 carbon number; X is a halogen atom; N=1～4,
Alcohol compound wherein means the alcohol compound with following ordinary construction formula (VII):
R
6For taking from any monovalent organic radical of 1～20 carbon number; Carbochain then be straight or branched all can, also can mix two or more alcohols and participate in reaction,
Wherein the organo-aluminium compound that mixes with alcohol compound (VII) means the organo-aluminium compound with following ordinary construction formula (VII):
R
7For taking from any monovalent organic radical of 1～8 carbon number; X is a halogen atom, hydrogen atom or alkoxyl group; 0＜n＜3,
The mixture (c) of alcohol compound wherein (VII) and organo-aluminium compound (VIII) ties up under 0～150 ℃ and reacts, and the time is 30 minutes to 300 minutes, and wherein alcohol is R with the ratio of aluminium
6OH: Al-R
7=0.1～10: 1, the alcohols of selection and organo-aluminium compound have more than and are limited to a kind ofly, can respectively select more than one to mix use mutually,
Resultant of reaction wherein (d) is that the mixture (c) of alcohols and organo-aluminium compound is got with resultant of reaction (b) contact reacts, and being reflected at 0～150 ℃ carried out 30 minutes～300 minutes, and Al wherein: Mg=0.1～20: 1,
Solid catalyst wherein (A) is to get with titanium halogen compound (VI) and resultant of reaction (b) or resultant of reaction (d) contact reacts, and being reflected at-30～150 ℃ carried out 30 minutes～300 minutes, wherein Ti: Mg=1～20: 1,
Organo-aluminium compound wherein (B) means the organo-aluminium compound with following ordinary construction formula (IX):
R
8For taking from any monovalent organic radical of 1～8 carbon number; X is a halogen atom, hydrogen atom or alkoxyl group; N=1～3.
Solid catalyst wherein (A) is Ti: Al=1 with the contact reacts ratio of organo-aluminium compound (B): 1～1000 grammeatom ratio, and the copolymerization of the polymerization of ethene or ethene and alpha-olefin, its temperature of reaction ties up to 30 ℃～200 ℃, and pressure is at normal pressure～50Kg/cm
2Hydrogen equimolecular quantity conditioning agent, account for 1～80% of reaction total pressure, the content system of organo-aluminium compound in the polymerization (B) is to contain aluminium 0.1～50 mmole person in every liter of solvent, alpha-olefin during copolymerization means the straight or branched alpha-olefin of 1～8 carbon number, and its add-on is 0～10% weight fraction.
2, by the method for claim 1, it is characterized by: the organic diacid series of compounds is selected from: Fu acid, propanedioic acid, oxalic acid, terephthalic acid and relevant group organic diacid compound thereof.
3, by the method for claim 1, it is characterized by: the anhydrous compound system of organic diacid compound is selected from: Fu acid anhydride and relevant group organic acid anhydride compound thereof.
4, by the method for claim 1, it is characterized by: organic diacid ester cpds system is selected from: diethyl phthalate ， Fu acid di-n-butyl, Diisopropyl malonate, propanedioic acid di-n-butyl and relevant group organic diacid ester cpds thereof.
5, by the method for claim 1, it is characterized by: the hydrogenation polysiloxane series is selected from: hydrogenated methyl polysiloxane and relevant group silicoorganic compound thereof.
6, by the method for claim 1, it is characterized by: organo-magnesium compound system is selected from: normal-butyl chlorination magnesium and relevant group organo-magnesium compound thereof.
7, by the method for claim 1, it is characterized by: titanium halogen compound system is selected from: titanium tetrachloride and relevant group titanium halogen compound thereof.
8, by the method for claim 1, it is characterized by: organo-aluminium compound (B) is selected from: triethyl aluminum and relevant group organo-aluminium compound thereof.
9, by the method for claim 1, it is characterized by: copolymerization refers to ethene and the alpha-olefin copolymer person of closing, and alpha-olefin wherein is: 1-butylene etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90103217A CN1042034C (en) | 1990-06-26 | 1990-06-26 | Catalyst synthesis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90103217A CN1042034C (en) | 1990-06-26 | 1990-06-26 | Catalyst synthesis |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98107418 Division CN1199054A (en) | 1998-04-20 | 1998-04-20 | Catalytic synthesis process |
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| Publication Number | Publication Date |
|---|---|
| CN1057846A true CN1057846A (en) | 1992-01-15 |
| CN1042034C CN1042034C (en) | 1999-02-10 |
Family
ID=4877980
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90103217A Expired - Fee Related CN1042034C (en) | 1990-06-26 | 1990-06-26 | Catalyst synthesis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258174B (en) * | 2005-09-07 | 2010-09-29 | 伊奎斯塔化学有限公司 | Olefin polymerization catalyst system |
| CN102898558A (en) * | 2011-07-26 | 2013-01-30 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898556A (en) * | 2011-07-26 | 2013-01-30 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898557A (en) * | 2011-07-26 | 2013-01-30 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898555A (en) * | 2011-07-26 | 2013-01-30 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| WO2023221562A1 (en) * | 2022-05-18 | 2023-11-23 | 中国科学院化学研究所 | Catalyst solid component for olefin polymerization, preparation method therefor and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5536235A (en) * | 1978-09-06 | 1980-03-13 | Nissan Chem Ind Ltd | Preparation of highly stereoregular polyolefin |
| JPS5883006A (en) * | 1981-11-13 | 1983-05-18 | Mitsui Petrochem Ind Ltd | Polymerization of olefin |
-
1990
- 1990-06-26 CN CN90103217A patent/CN1042034C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258174B (en) * | 2005-09-07 | 2010-09-29 | 伊奎斯塔化学有限公司 | Olefin polymerization catalyst system |
| CN102898558A (en) * | 2011-07-26 | 2013-01-30 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898556A (en) * | 2011-07-26 | 2013-01-30 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898557A (en) * | 2011-07-26 | 2013-01-30 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898555A (en) * | 2011-07-26 | 2013-01-30 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898556B (en) * | 2011-07-26 | 2015-06-17 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898558B (en) * | 2011-07-26 | 2015-06-17 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898557B (en) * | 2011-07-26 | 2015-06-17 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| CN102898555B (en) * | 2011-07-26 | 2015-06-17 | 中国石油化工股份有限公司 | Application of catalyst component in olefin polymerization |
| WO2023221562A1 (en) * | 2022-05-18 | 2023-11-23 | 中国科学院化学研究所 | Catalyst solid component for olefin polymerization, preparation method therefor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1042034C (en) | 1999-02-10 |
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