CN1047305A - Form of spherical particles at high porosity crystalline propene polymer and multipolymer - Google Patents

Abstract

Have porosity (representing with percentage of voids) more than 15%, surface-area is between 10-20 rice ²The crystalline polymers of propylene and the multipolymer of the spherical particle shape of/gram (B.E.T) face.These polymkeric substance are particularly useful for making the masterbatch that contains significant quantity additive and/or pigment.

Description

Form of spherical particles at high porosity crystalline propene polymer and multipolymer

To the present invention relates to have median size be the 50-7000 micron and have porosity and the spherical particle shape crystalline propene polymer and the multipolymer of surface-area characteristic, and these characteristics make it to be suitable for preparing the masterbatch that contains significant quantity pigment and/or additive.

People know, can obtain be used for the catalyst component of olefinic polymerization with the spherical particle form, and this form is suitable for improving the optimal morphology characteristic of polymkeric substance, and this catalyst component contains with activity form and is stated from titanium compound on the magnesium halide.

This class catalyst component is disclosed in United States Patent (USP) 3953414 and 4399054, and particularly the polymkeric substance that obtains with the catalyzer of introducing in the United States Patent (USP) 4399054 is a spherical particle shape, and it is mobile and the apparent density value is higher.But its porosity (represent with percentage of voids, be about 10%) and surface-area are not enough height, therefore can not make it to be used to prepare the interested field of containing the masterbatch of significant quantity pigment and/or additive of people.

Have now found that, can with spherical-like morphology obtain isotactic index greater than 90 homopolymer polypropylene and contain weight greater than 85%() propylene and the ethene and/or the CH of propylene ₂The crystalline copolymer of=CHR alkene, wherein R is the alkyl of 2-8 carbon atom.The median size of above-mentioned spherical particle form is the 50-7000 micron, and the porosity of representing with percentage of voids is preferably 15-30% greater than 15%.

The distribution of pore volume is that the aperture in the hole more than 90% is greater than 10000 Surface-area is greater than 10 meters ²/ gram, preferred 10-20 rice ²/ gram.For example, representative polymkeric substance has following character:

Surface-area: 10-20 rice ²/ gram,

Porosity: 15-30%,

The distribution of size of particles: the diameter of 100% particle is the 1000-3000 micron, and the diameter of preferred 40-50% particle is the 1000-2000 micron, and the diameter of 35-45% particle is the 2000-3000 micron.

Polymkeric substance of the present invention is particularly useful for making the masterbatch that contains significant quantity additive and/or pigment.(comprising the halogenide, halogenation dealing with alcohol titanium and the electronic donor compound capable that are stated from the magnesium chloride) obtain being used to prepare the catalyzer of polymkeric substance with catalyst component with specific form character.

This catalyst component is that the adducts by magnesium chloride and alcohols obtains, in this adducts, and every mole of MgCl in general ₂Contain 3 mol of alcohol.This catalyst component is preparation like this, under the melting attitude, above-mentioned adducts put into the immiscible inert liquid hydrocarbon of melting adducts carry out emulsification, then, in order to make this adducts be cured as spherical particle shape, emulsification is cooled off in a short period of time.Under 50-130 ℃, heating cycle is carried out the part dealcoholysis with these particles, until pure content is dropped to 0.5-1.5 moles/mole MgCl from 3 moles ₂Again thus obtained adducts is suspended in cold TiCl ₄In, concentration is the 40-50 grams per liter, is incubated 1-2 hour down at 80-135 ℃ then.At TiCl ₄In also add the electronic donor compound capable of preferentially from O-phthalic acid alkyl ester, cycloalkyl ester or aryl ester, selecting, as o-benzene butyl phthalate ester, di-n-butyl ester and di-n-octyl ester.Remove excessive TiCl while hot by filtering or precipitating then ₄, and use TiCl ₄The re-treatment one or many.Solid is carried out drying after with heptane or hexane wash again.The catalyst component that makes with this method has following characteristic:

Surface-area: less than 100 meters ²/ gram, preferential 60-80 rice ²/ gram,

Porosity (nitrogen): 0.25-0.35 centimetre ³/ gram,

Pore volume distribution: the pore radius more than 50% is greater than 100

Catalyzer makes like this, with solid catalyst component and trialkyl aluminium compound (preferential triethyl aluminum and triisobutyl aluminium) and be R ' R preferentially from molecular formula " Si(OR) ₂Silane compound in the electronic donor compound capable selected mix, at R ' R " Si(OR) ₂In, " being identical or inequality, is alkyl, cycloalkyl or the aryl of 1-8 carbon atom, and R is the alkyl of 1-4 carbon atom for R ' and R.

Also can use silane resemble the phenyl triethoxysilane.Dimethoxydiphenylsilane, two cyclohexyl methoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane are wherein representational silane.

The ratio of Al/Ti generally between 10-800, silane/Al(mol ratio) between 1/5-1/50.

Can adopt known operative technique in liquid monomer or gas phase, to carry out the polymerization of propylene.

Temperature between 70-90 ℃ is to carry out the preferred temperature of polymeric.Catalyzer can be contacted (prepolymerization) in advance with a spot of alkene, catalyzer be maintained be suspended in the hydrocarbon solvent, temperature is carried out polymerization between room temperature-60 ℃, by weight, the amount of the polymkeric substance of generation be catalyzer 0.5-3 doubly.Operation also can be carried out in monomer liquid, and the amount of the polymkeric substance of Sheng Chenging is up to 1000 times (weight meters) of catalyzer in this case.

Masterbatch is prepared by some known technologies.The main points of one of them are to make polymkeric substance be absorbed in additive (pigment) solution or emulsion in a certain solvent, boil off solvent then.The amount of the additive that has absorbed depends on itself concentration in solution or emulsion.Wherein the main points of another kind of method are, absorb the additive or the additive agent mixture of melting attitude.Adopt these methods, under the situation of solution or emulsion, the amount of absorbent additive (pigment) is about about 10-15 weight %, and as absorbing the additive of melting attitude, the amount of absorbent additive (pigment) is in 20-30%(weight) about.Under the porous polymer situation, adopt known technology, the corresponding amount that is absorbed is no more than 2% and 4% respectively.

According to another kind of method, with additive and/or colo(u)rant dispersion in low-melting melting wax.Then with this dispersion and mixed with polymers, the blended amount makes the pigment that is scattered in the wax phase and/or additive coated on the said polymer, and adopting the amount that this kind method can fixed additive/pigment is 20-25%(weight) about.

The additive that can be used (pigment) is that those join the additive (pigment) that goes in the polymkeric substance usually in order to make polymkeric substance have property.They comprise stablizer, filler, titanium dioxide, iron protoxide, phthalocyanine etc.

The data of reporting in embodiment and text that relate to following character are measured with following method: the character method

MIL fluidity index ASTM-D1238

Be dissolved in dimethylbenzene

In part (seeing note)

Be not dissolved in polymkeric substance (the % weight in the dimethylbenzene under the isotactic index room temperature (25 ℃)

Amount) (is substantially equal to not be dissolved in the polymerization in the boiling n-heptane

Thing % weight)

Surface-area B.E.T(equipment therefor is SORPTOMATC1800-C.Erba)

Porosity (nitrogen) B.E.T(sees upward hurdle)

Apparent density DIN-53194

Mobile it be that 100 gram polymkeric substance flow through that diameter is arranged is 1.27 centimetres going out

The time that the funnel of oral pore is required.The slope of its wall and vertical direction

Degree is 20 °.

Form ASTM-D1921-63

Measure the porosity of representing with percentage of voids adding the way of depressing by absorbing mercury.The volume of the mercury that absorbs depends on the volume in hole.In order to carry out this mensuration, adopt and mercury storage tank and high vacuum rotor pump (1 * 10 ^-2Mba) probe (3 millimeters of diameters) CD3(C.Erba is checked and approved in having of connecting) dilatometer measure.Packing in dilatometer claims overweight sample (about 0.5 gram), makes this dilatometer be under the high vacuum (＜0.1 mmhg) then and keeps 10 minutes, and it is connected relief mercury slowly to flow into until the scale that is marked on probe be 10 centimetres with the mercury storage tank again.Close the valve that connects dilatometer and vacuum pump, charge into nitrogen this dilatometer is under the 2.5 kg/cm pressure, this pressure makes in the mercury infiltration hole and the scale value on the probe is reduced according to the porosity of material.As long as determined the new mercury scale value of having stablized on the probe, just calculated the volume in hole: V=R by following formula ²π △ H, the R here are the radiuses with the probe of centimetre expression, △ H be initial and final height of mercury in centimetre difference, the volume of sample is calculated by following formula:

Vl＝ (P1-（P2-P）)/(D)

Wherein: P is the weight in grams number of sample,

P1 is the weight in grams number of dilatometer and mercury,

P2 is the weight in grams number of dilatometer, mercury and sample,

D is that the density of mercury (under 25 ℃, is 13.546 gram per centimeters ³),

Porosity is calculated by following formula:

X＝ (100·V)/(Vl)

Note: under the room temperature, the polymer moieties that is dissolved in the dimethylbenzene measures as follows:

Stir down, restrain polymer dissolution in 135 ℃ dimethylbenzene (250 milliliters) 2.After 20 minutes, it is cooled to 25 ℃, and continues to stir always, left standstill thereafter 30 minutes.Leach precipitation with filter paper, then in nitrogen gas stream with solution evaporation, at 80 ℃ of following vacuum-drying resistatess until constant weight.Calculate the weight percent that is dissolved in the polymkeric substance in the dimethylbenzene under the room temperature then.

Embodiment 1

Press United States Patent (USP) 4,399, the method for introducing among 054 embodiment 2 prepares the spherical granular MgCl that diameter is the 30-150 micron ₂3C ₂H ₅The OH adducts.But, 000RPM(rev/min 5) under operate, rather than 10,000RPM.

Then under nitrogen gas stream, temperature is raised to 100 ℃ of heating from 50 ℃, this adducts is carried out dealcoholysis, reach 1.5 moles/mole MgCl until pure content ₂Its surface-area of adducts that obtains by this method is 9.1 meters squared per gram, and apparent density is 0.564 gram per centimeter ³Under 0 ℃, while stirring 25 gram adductss are added to 625 milliliters of TiCl ₄In, again in 1 hour internal heating to 100 ℃, when temperature reaches 40 ℃, in Mg/ o-benzene butyl phthalate ester two 8(mol ratios) ratio add o-benzene butyl phthalate ester.In 2 hours, be heated 100 ℃ again, make its precipitation and siphon while hot go out liquid then, add 550 milliliters of TiCl ₄, be heated 120 ℃ in 1 hour.Make its precipitation and siphon while hot go out liquid then.

Under 60 ℃, with 200 milliliters of anhydrous hexanes with this solids wash 6 times, washing 3 times under room temperature then.This solid after the vacuum-drying has following characteristic:

Porosity (nitrogen): 0.389 centimetre ³/ gram;

Surface-area: 221 meters squared per gram;

Apparent density: 0.555 gram per centimeter ³

DIBF:6.8%(weight),

Surface-area: 66.5 meters squared per gram,

Porosity (nitrogen): 0.261 centimetre ³/ gram,

Apparent density: 0.440 gram per centimeter ³

According to using the resulting 412 gram polymkeric substance of the above-mentioned catalyst component of 0.023 gram to have following character in the propylene polymerization of embodiment 1:

Be dissolved in the part in the dimethylbenzene: 3%,

MIL:2 gram/10 minutes,

Apparent density: 0.35 gram per centimeter ³,

Percentage of voids: 23.5%,

Form: 100% spherical particle, its diameter is between 500-

Between 5000 microns,

Mobile: 12 seconds.

Embodiment 3

Under 120 ℃, test resulting 20 kilograms of spherical particle polypropylene adopting the resulting catalyzer of pointing out among the embodiment 2 of catalyst component by continuous propylene polymerization, packing in the LOEDIGE FM130P mixing tank of carrying vapour, is under 150 rev/mins it to be mixed to reach 70 ℃ until polymer temperature in 5 minutes in paddle speed.Then in 120 ℃ of 5 kilograms of ATMER163(ATLAS that spray down).Continue to stir 15 minutes, with the product discharging.The polymkeric substance that obtains is a spherical particle, and all particle diameters all between between the 1000-5000 micron, contain 19.8%(weight) ATMER, polymer flow is 13 seconds.

0.01 this solid of gram is used for the propylene polymerization experiment as follows.4 liters of autoclaves that agitator and constant temperature system are housed are being washed with propylene after 1 hour with nitrogen wash under 70 ℃ in advance again, then under 30 ℃, do not stir but the catalyst system of in flow of propylene, packing into, this catalyst system is by being to be suspended in 80 milliliters of catalyst components in the hexane, and 0.76 gram triethyl aluminum and 8.1 milligrams of dimethoxydiphenylsilanes are formed.This catalyst system is just to prepare before the experiment.Close autoclave then, input 1Nl hydrogen stirs 1.2 kilograms of liquid propenes of adding down, makes temperature be raised to 70 ℃ within 5 minutes, and makes it constant temperature 2 hours, when experiment finishes, stops to stir, and removes unreacted propylene.Behind the autoclave cool to room temperature, reclaim polymkeric substance, under 70 ℃, be dried 3 hours with baking oven in the nitrogen gas stream, the 378 gram polymkeric substance that make have following character:

Be dissolved in the part in the dimethylbenzene: 2.6%;

MIL:2.8 gram/10 minutes;

Apparent density: 0.375 gram per centimeter ³;

Percentage of voids: 16%;

Surface-area: 10 meters squared per gram.

Embodiment 2

From the MgCl that obtains as embodiment 1 ₂3C ₂H ₅Remove ethanol until MgCl in the OH adducts ₂/ C ₂H ₅The ratio of OH is 1.The adducts surface-area of Huo Deing is 11.5 meters squared per gram like this, and apparent density is 0.535 gram per centimeter ³

Under the condition of in embodiment 1, pointing out and TiCl ₄The spherical pelleted catalyst composition that the adducts of reaction makes has following characteristic:

Ti=2.2%(weight),

Claims (3)

1, isotactic index is greater than 90 alfon and propylene and ethene and/or CH ₂The crystalline copolymer of=CHR alkene (R is the alkyl of 2-8 carbon atom) (containing the above propylene of 85% (weight)), above-mentioned polymkeric substance is the average even spherical particle of diameter between the 50-5000 micron, the porosity of representing with percentage of voids is greater than 15%, and surface-area (B.E.T) is between 10-20 rice 2/ gram.

2, propene polymer as claimed in claim 1 and copolymer pellet, its percentage of voids are between 20-30%, and its surface-area is between 10-20 rice ²Between/the gram.

3, contain 10-30%(weight as above-mentioned arbitrary claim) polymer beads of additive and/or pigment.