JPS5846469B2 - Composite materials and their manufacturing methods - Google Patents

Description

[Detailed description of the invention] The present invention relates to a composite material and its manufacturing method.

This composite material is used in the construction materials industry as an aggregate for lightweight concrete.

Composite materials known in the prior art fill the pores of a porous solid carrier concrete with low molecular weight (less than 70,000) polyethylene, the filling rate of polyethylene relative to the total volume of the pores being 0.5-1.0%. (Soviet inventor certificate No. 39
No. 4340, IPCC04B41104).

Another method of making this composite material known in the prior art is to impregnate a porous solid carrier concrete with a solution or melt of low molecular weight polyethylene (Id. Inventor's Certificate).

Due to the high viscosity of the solutions and melts, it is difficult to fill the pores of the carrier to the required extent.

(In the above inventor's certificate, only 0.5% of the total volume of carrier pores
~It is stated that it only fills the section 1.0)
.

The smaller the diameter of the pores, the lower the filling capacity of the pores.

This drawback leads to unsuitable properties of the composite materials produced, ie to low resistance to frost and moisture.

Composite materials known in the prior art also fill the pores of a porous solid carrier, for example ceramsite, with polyethylene or polyacrylate.

The weight ratio of carrier:polymer is 97:3 (U.S. Pat.
, No. 567.496, C1117-113).

Composite materials known in the prior art are made by impregnating a porous solid support, e.g. expanded clay, with a liquid monomer or solution of monomer, e.g. styrene, acrylic acid or its derivatives, and a free-radical polymerization initiator. After this, the monomers within the carrier pores are polymerized by heat or radiation (ibid. patent).

No matter which polymer is used in this method, it is not possible to control the filling of pores, so it is difficult to obtain a composite material having the above properties.

An object of the present invention is to provide a composite material with excellent strength, frost resistance, and hydrophobicity.

Another object of the invention is to provide a method for producing a composite material having the above properties.

These and other objects of the present invention are to form pores in porous inorganic particles (hereinafter referred to as carriers) with a molecular weight of 300,
This can be achieved by a composite material in which 4 or more of the total volume of the pores is filled with a polyolefin having a molecular weight of 0.000 or more and a weight ratio of carrier:polymer of 50 to 99.5.

The composite material of the present invention has high strength (compressive strength 100-2
00kg/crit).

A feature of this material is its great frost resistance.

(Withstands 540 frost cycles without destruction,
This corresponds to 180 fields.

This frosting and inkstone box cycle begins at -2 to -3℃ with 4
h cool then heat at 20° C. for 4 h).

Furthermore, the material of the present invention has high hydrophobicity (hydrophobicity is measured by the amount of water absorbed at a temperature of 20°C. The carrier:polymer weight ratio is 93 nia, and the water absorption rate is 0.1 weight range).

Another object of the present invention is to deposit a composite organometallic compound catalyst consisting of a transition metal compound and an organic compound of Group 2 or 3 metal of the periodic table on porous inorganic particles from the gas phase, Polymerizing olefins from the gas phase at 50 to 165° C. and a pressure of 1 to 60 atmospheres, at which time the catalyst is deposited in two stages, in the first stage the first fraction of the catalyst, that is, the transition metal compound is deposited, In the second stage, the second component of the catalyst, i.e. an organic compound of a group 2 or 3 metal of the periodic table, is deposited, and the first component of the catalyst is deposited from the gas phase at a temperature of 20-300°C and a pressure of is 0.
05 to 1.2 atmospheres, then increased by at least 30 parts of this pressure, and then lowered to at least the initial pressure, and the second fraction of the catalyst is deposited from the gas phase at a temperature of 20 parts.
This can be achieved by a composite manufacturing process carried out at ~165°C.

Prior to the polymerization reaction, the components of the catalyst can be deposited into the pores of the porous solid support in the order listed above.

Also, before the polymerization reaction, the first component of the catalyst, that is, a transition metal compound, is deposited in the pores of the porous solid support, and the second component of the catalyst, that is, an organic compound of a group 2 or 3 metal of the periodic table, is deposited. It is possible to carry out a polymerization reaction at the same time.

In order to improve the frost resistance, mechanical strength and hydrophobicity of this composite material, after the polymerization reaction it is recommended to treat the obtained composite material at a temperature of 120-200° C. for 10-30 minutes.

The high grade composite material obtained by the method of the invention has a predetermined set of properties.

By the method of the present invention, it is possible to control the filling rate of the carrier pores with the polymer over a wide range (4 factors or more of the total volume of the pores), and other properties of the resulting composite material can also be controlled. Can be controlled over a wide range.

The polyolefins used in the composite materials of the invention are, for example, polyolefins such as polyethylene, polypropylene, polyisobutylene, polymethylpentene, and copolymers of various olefins, such as ethylene-propylene copolymers.

The porous solid carrier used in the composite material of the present invention is, for example, ceramisite, baked clay, expanded perlite, foamed glass, tripolite, porous slag, and the pore size of the carrier is (from 1μ to several ) can vary widely.

The raw material olefins used in the method for producing the composite material of the present invention are, for example, ethylene, propylene, butene, and methylpentene.

Olefins can be used alone or in various combinations thereof in this process.

The method for producing the composite material of the present invention can be carried out as follows.

If necessary, the porous support is dried for 1 to 3 h at a temperature of 100 to 300° C. before entering the reactor.

The support is then placed in a reactor and purged with inert gas or vacuumed.

Next, the vapor of the transition metal compound (the first component of the composite organometallic compound catalyst) is sent to the reactor alone or together with an inert gas.

The temperature of the reaction system varies depending on the nature of the transition metal compound.
The pressure of the gas system is initially 0.
．． 0.05 to 1.2 atmospheres, then increased by at least 30 times the initial pressure, and then lowered to at least the initial pressure.

During this time, the pores of the porous solid support are filled with the vapor of the transition metal compound alone or as a mixture of the vapor and the carrier gas,
A first component of the catalyst is deposited into the pores of the support.

Depending on the type of porous solid body and the pore filling rate by the polymer, the transition metal compound to be deposited in the pores ranges from 0.001 to 0.05 weight range of the porous support.

One cycle is sufficient for the rise and fall of pressure, but when the diameter of the pores in the solid mallet is small, this cycle may be repeated once.
It can be repeated once, twice, etc.

Immediately after depositing the first component of the composite organometallic compound catalyst into the pores of the carrier, the second component of the catalyst, ie, an organic compound of a group 2 or 3 metal of the periodic table, is introduced into the reactor.

The temperature inside the reactor is maintained in the range of 20-165°C.

The organometallic compound is introduced as a gas into the reactor together with a stream of inert carrier gas or with a stream of gaseous monomer.

At least the second component of the catalyst is introduced into the reactor in an amount equal to the amount of the first component deposited.

The optimum amount of the second component of the catalyst is between 0.003 and 0.00% of the weight of the carrier.
It is 15%.

The second fraction of the catalyst introduces this vapor, alone or together with a stream of inert gas (carrier gas), into the reactor to deposit the second component of the catalyst prior to the polymerization reaction.

Immediately upon depositing the second component into the pores of the support, a complex organometallic compound catalyst is formed to polymerize the olefin.

For this purpose, an olefin is introduced into the reactor at a temperature of 50 to
Polymerization is carried out from the gas phase at 165° C. and a pressure of 1 to 60 atmospheres.

When the vapor of the second component of the catalyst is introduced into the reactor together with the monomer gas stream, the second component is deposited in the pores of the carrier and simultaneously a polymerization reaction occurs.

It is recommended that the deposition of the first and second components of the catalyst and the polymerization of the olefin be carried out while stirring the porous solid support.

This agitation can be achieved by fluidized bed or flow bed, mechanical agitation or gravity,
This can be done by stirring by air or vibrational motion.

The pore filling rate by the polymer is the required value (4 of the total volume of pores).
When this temperature is reached, the pressure of the monomer is lowered (by ceasing the introduction of the monomer into the reactor) or the temperature is lowered to stop the polymerization reaction.

The product (composite material) is then cooled if necessary and removed from the reactor.

The degree of pore filling by the polymer can be varied over a wide range by varying the temperature, pressure and time of the reaction.

In order to improve the strength, frost resistance and hydrophobicity of this composite material, it can be further heat treated at a temperature of 120-250<0>C for 10-30 minutes.

During this treatment, the polymer melts within the carrier pores and closes them.

A further understanding of the invention may be provided by the following examples which illustrate embodiments of the invention.

Example 1 Ceramsite stone (particle size 15-20cm, bulk density 500k)
g/6 Compressive strength 28 kg/1, total porosity 50% by volume) 9
After drying 2 kg at a temperature of 200°C, it was placed in a reactor.

After the reactor was evacuated, 4.1 g of vanadium tetrachloride was introduced into the reactor as a vapor at a temperature of 20° C. together with a nitrogen stream.

The pressure of the gas in the reactor was initially 01 atm, then 05 atm.
The pressure was increased to atmospheric pressure and allowed to fall to the initial value over a period of 1-2 minutes.

Through this operation, vanadium tetrachloride was deposited in the mallet cavity.

Then, at a temperature of 20° C., diethylaluminum chloride (12 g) was introduced as a vapor into the reactor along with a stream of ethylene.

The reactor temperature was maintained at 50°C and the ethylene pressure rose to 60 atmospheres.

The polymerization of ethylene was carried out at this specific temperature and pressure, and the entire reaction was completed in 120 minutes.

When the polymerization was completed, the unpolymerized ethylene in the reactor was purged with nitrogen, and the resulting product was taken out.

The obtained composite material contained 8.4 kg of polyethylene, had a filling ratio of 18 to the total volume of pores, and had a porous carrier:
The weight ratio of polymers in the composite was 91:9.

The molecular weight of the polymer was 700,000.

The compressive strength of this composite material was 130 kg/-.

To determine the frost resistance of composite materials, first
The mixture was cooled for 4 h at 20° C. and then heated at 20° C. for 4 h.

The composite material remained intact even after 500 cooling and heating cycles.

In contrast, the unfilled ceramsite stone was destroyed after 15 cycles.

The moisture absorption rate of this composite material was 0.3 weight.

On the other hand, the moisture absorption rate of the raw material carrier (not impregnated with polyethylene) was 24% by weight.

Further, in order to improve the strength, frost resistance and hydrophobicity of this composite material, the obtained composite material was placed in a reactor and heated at a temperature of 190° C. for 10 minutes.

The characteristic values of the composite material subjected to this heat treatment are compressive strength 1
52kg/ffl, frost resistance 540 times, moisture absorption rate 0.05
It was a heavy duty type.

Example 2 Raw material Tripoli stone (particle size 10-15 mm, bulk density 600
6 kg/i, compressive strength 56 kg/i, total porosity 30 volume ratio, moisture absorption rate 17 weight placement frost resistance 20 times: 190 kg was placed in a reactor and dried at a temperature of 200°C.

After cooling the reactor to 165° C. and applying vacuum, 3 (l) of vanadium tetrachloride was introduced into the reactor with a stream of nitrogen.

The pressure of the gas in the reactor was initially set to 0.5 atm, which was raised to 0.7 atm and then lowered to 0.3 atm to deposit vanadium tetrachloride into the carrier pores.

40 g of triethylaluminum vapor was introduced into the reactor at a temperature of 1650 C with a nitrogen stream.

Propylene was then introduced into the reactor to bring the pressure to 20 atmospheres.

Propylene was polymerized at a temperature of 165°C.

The total time for the polymerization reaction was 90 minutes.

The reactor was then cooled and purged of unpolymerized propylene with nitrogen.

The resulting composite material was removed from the reactor.

This composite material contained 0.95 kg of polypropylene, the filling ratio of the pores to the total volume was 4, and the weight ratio of porous carrier:polymer was 99.3:0.7.

The molecular weight of the polymer was 300,000. The composite material had a compressive strength of 80 kg/crtt, a frost resistance of 340 times, and a moisture absorption rate of 0.12.

Example 3 1.3 kg of granular expanded perlite (particle size between 3 and 10, bulk density 270 kg/m3, compressive strength 14.2 kg/i, total porosity 83 volume ratio, moisture absorption 40% by weight) was placed in a reactor. and dried at a temperature of 200°C.

Next, vacuum the reactor and at the same time lower the temperature inside the reactor to 90°C.
The temperature was lowered to ℃.

After stabilizing the temperature inside the reactor, 1.3 g of titanium tetrachloride was introduced as vapor together with a nitrogen stream.

The gas pressure in the reactor was initially 0.07 atm.

The pearlite in the reactor is stirred by gravity by rotating the reactor, and the pressure of the gas in the reactor is raised to 1 atm, and then lowered to 0.7 atm again.
After introducing g of vapor into the reactor with a nitrogen stream, a 4:1 molar mixture of ethylene and α-butene was introduced into the reactor.

After the copolymerization reaction was carried out at a temperature of 90°C, a pressure of 1 atm, and a reaction time of 15 h, the reactor was purged with nitrogen, and at the same time the temperature was 20°C.
It was cooled to

The resulting composite material was removed from the reactor. The composite material contained 0.32 kg of ethylene and alpha-butene copolymer.

The filling ratio with respect to the total volume of pores was 9 parts, and the weight ratio of porous carrier (expanded perlite) to copolymer was 85:15.

The molecular weight of the copolymer was 300,000.

This composite material had a compressive strength of 25 kg/cit, a frost resistance of 400 times, and a moisture absorption rate of 1.0 by weight.

Example 4 Ceramsite stone (particle size between 15 and 20, bulk density 500 kg/m, compressive strength 28 kg/i, total porosity 50
Volume control, frost resistance 15 times) 72 kg, nitrogen 15 times
After purging for a minute, the reactor was heated to 70° C. and vanadium oxytrichloride was introduced as vapor with a stream of nitrogen.

The pressure of the gas in the reactor was initially 1.2 atm, then increased to 2.0 atm, and then lowered to 1.2 atm again.

Vanadium oxytrichloride was thus deposited inside the carrier pores.

5 g of triisobutylaluminum was introduced as vapor into the reactor along with a stream of ethylene.

Polymerization of ethylene occurred simultaneously with the deposition of triisobutylaluminum into the carrier pores.

The pressure of ethylene in the system was 5 atmospheres.

The polymerization reaction was carried out at a temperature of 70°C and the specified pressures mentioned above.

The total time of polymerization was 4.5 h. When the polymerization reaction is finished,
The reactor was purged with nitrogen, cooled to 20° C., and the resulting composite was removed.

This composite material contained 4.5 kg of polymer, the filling ratio of the pores to the total volume was 12, and the porous carrier:polymer weight ratio was 94:6.

The molecular weight of the polymer was 700,000-750,000.

This composite material had a compressive strength of 70 kg/crlt, a frost resistance of 500 times, and a moisture absorption rate of 0.21.

Example 5 Foamed glass (particle size 5-10M) dried at 200°C
! Butt, bulk density 40kg/m, compressive strength 0.5ky/c
yit1 total porosity 90 volume ratio) 1.2ky was put into the reactor.

After evacuating the reactor, the temperature was increased to 300°C.

While stirring the carrier constantly, 2 g of iron trichloride were introduced as vapor with a stream of nitrogen.

The system pressure was initially set to 0.5 atm, then increased to 1 atm, and then lowered to 0.6 atm.

Iron trichloride was thus deposited into the pores of the foam glass.

The reactor was then cooled to 70°C and 2.4 g of triisobutylaluminum was introduced as vapor into the reactor.

Ethylene was then introduced into the reactor to bring the pressure to 25 atmospheres.

Ethylene was kept at a temperature of 70°C and the above specified pressure for 3.5 hours.
It was kept and polymerized.

After the polymerization reaction was completed, the reactor was purged with nitrogen for 20
After cooling to 'C, the composite was removed from the reactor.

The obtained composite material contained polyethylene 1200.9, had a filling rate of 30% relative to the total pore volume, and a porous carrier:polymer ratio of 50:50.

The molecular weight of the polymer was 500,000.

Is the compressive strength of this composite material 5kg/cr? t, moisture absorption rate 1
．． The weight range was 0.

In order to improve the strength, frost resistance and hydrophobicity of the composite, the composite was placed in a reactor and maintained at a temperature of 120° C. for 30 minutes.

This was then cooled to 20°C and taken out from the reactor.

The new characteristic values of the composite material thus obtained were a compressive strength of 10 kg/criY1 moisture absorption rate of 0.5% by weight.

Claims (1)

[Claims] 1. The pores of the porous inorganic particles are filled with 4% or more of the total volume of the pores with a polyolefin having a molecular weight of 300,000 or more, and the weight ratio of the porous inorganic particles to the polyolefin is 50 to 50. 99.5: Composite material with a ratio of 50 to 0.5. 2 A composite organometallic compound catalyst consisting of a transition metal compound and an organic compound of Group 2 or 3 metal of the periodic table is deposited on porous inorganic particles from the gas phase, and the catalyst is heated at a temperature of 50°C on the catalyst.
Polymerization of olefins from the gas phase at ~165°C and a pressure of 1 to 60 atmospheres, with the catalyst being deposited in two stages: in the first stage the first component of the catalyst, i.e. the transition metal compound, is deposited, and in the second stage The second component of the catalyst, i.e., an organic compound of a group 2 or 3 metal of the periodic table, is deposited at a temperature of 20 to 300° C. and the pressure is initially 0.5° C. while the first component of the catalyst is deposited from the gas phase. 05~1.2 atm,
Then after increasing this pressure by at least 30%,
A process for producing a composite material, wherein the deposition of the second component of the catalyst from the gas phase is carried out at a temperature of 20 DEG to 165 DEG C., at least to an initial pressure. 3. The method for producing a composite material according to claim 2, wherein a catalyst component is deposited in the pores of the porous inorganic particles before the polymerization reaction. 4. Before the polymerization reaction, the first component of the catalyst, that is, a transition metal compound, is deposited in the pores of the porous inorganic particles, and the second component of the catalyst, that is, an organic compound of a group 2 or 3 metal of the periodic table, is deposited. The method for producing a composite material according to claim 2, wherein a polymerization reaction is simultaneously carried out. 5 After the polymerization reaction, the obtained composite material was heated to a temperature of 120 to 2
The method for producing a composite material according to any one of claims 2 to 4, wherein the composite material is processed at 00°C for 10 to 30 minutes. 6. The method for producing a composite material according to any one of claims 2 to 5, characterized in that the inorganic particles are ceramsite stone, tripolite, expanded pearlite, or foamed glass.