• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    An improved process for chlorinating high density polyethylene "in bulk" is described, with a two-stage reaction, the first at temperatures below the crystalline melting point, and the second above that temperature, and using a polyethylene starting material having a critical combination of characteristics, as described.
    公开号:SU786908A3
    申请号:SU782579204
    申请日:1978-02-15
    公开日:1980-12-07
    发明作者:Адольф Альберт Схоен Ловхард；Ян Ван Асперен Питер；Герард Мари Брблс Вильхельм；Антони Мари Дебетс Вильхельм
    申请人:Стамикарбон Б.В. (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to the technology of chlorinated ethylene production. It can be used in the petrochemical industry.
    A method of producing chlorinated polyethylene is known by treating with chlorine a mass of finely divided polyethylene at 15-160 ° C and 0.1-10 kg / cm flT. In this case, the chlorination is carried out in bulk at rather high temperatures. However, the disadvantage of this method is that the chlorination proceeds too quickly in the initial phase, while the reaction is ecoelectric. In the case of the chlorination of finely distributed polyethylene without solvent or in suspension, local overheating easily occurs and as a result, the reaction rate in these places increases, which leads to an increase in heat generation contributing to the formation of melt and lumps, as well as decomposition and even burning. This is accompanied by an undesirable darkening of the product.
    The purpose of the invention is to prevent sintering of polymer particles in the chlorination time.
    This goal is achieved by the fact that. To the known method of producing chlorinated polyethylene by treating with chlorine a mass of finely ground polyethylene at 15–160 ° C and 0.1–10 kg / cm, a starting polymer is used that contains: 0–5 mol% of Cz – Ce – alkenes and has a density of 0.93-0.97 g / cm, melt index 0.01-5, porosity
    0 0,005-0,15, specific surface 0.1-1 and the wax content up to 1 wt.%.
    The process can be carried out sequentially in two stages: first, at a temperature below the melting point of the crystallite, at 25–105 ° C, and then, at a temperature above the melting point of the crystalline polyethylene, at
    20 11 ° -150 ° C. In addition, during chlorination, water or liquid chlorine can be sprayed or sprayed into the reaction mass.
    By wax is meant a fraction of polyethylene soluble in boiling hexane. The wax content is determined by extracting it from polyethylene with hexane in a Soxhlet apparatus.
    The melt index is determined by
    30 IASTM D-1238, Condition E, and is the amount of polyethylene in grams, extruded for 10 under standard conditions through a standard capillary.
    The granulometric composition is determined by a sieve analysis of particles thinner than 50 μmc less than 1% by weight and particles larger than 2000 mmk less than 1% by weight. Preferably, the particle size distribution is in the range of 50 to 2000 microns. A narrower distribution, for example 90% or more in the region from 50 mmk or less, preferably to a wide distribution, for example, practically covering the whole region 50-2000 mmk The preferred particle size distribution is from 50 to 700 mmk.
    Porosity is determined by the mercury indentation method. Guiller, Bohlen and Guiller, Helv Chim. fteta 42, 2103 (1959); L. de Vita and J. Scholten in the Journal of Catalusis 36,36-47 1975.
    The specific surface area (BET) is determined according to the method described by% J. Am. Chem. Soc. 60 (1938) 309,
    The chlorination according to the invention is carried out at temperatures of 15-160 ° C and chlorine partial pressures from. 0.1 to 10 ata. In the first stage (i.e., below the melting point of the crystallite) chlorination {s) occurs at temperatures of 25-105 ° C. preferably 75-100 ° C. In the second stage (i.e., above the melting point of the crystallite), chlorination occurs at temperatures of 110-150 ° C, preferably 135-150 ° C. Chlorine can be diluted with inert gases, for example hydrogen chloride, water vapor and noble gases, etc.
    According to the invention, chlorinated polyethylene powder can be obtained with different chlorine content - from 5 to 70% by weight, preferably from 10 to 50%. More often get this powder with a chlorine content of from 30 to 48% by weight.
    Chlorination can be carried out in a fluidized bed, in a moving bed of a horizontal stirred reactor, in a rotating drum and in another known device for the reaction between gases and solids. To obtain a homogenously chlorinated product, the ethylene polymer must be continuously stirred to ensure a constant supply of chlorine and removal of hydrogen chloride. Chlorination can be carried out in the presence of radical-forming initiators or under the action of radiation, but this is not necessary. Typically, the radical-forming radiation is light with a wavelength of 30004500L. Suitable radical-initiating initiators are: peroxides and hydroperoxides, for example, peroxide.
    benzoyl, diisopropyl peroxydicarbonate, benzoyl hydroperoxide, cumene hydroperoxide, lauryl hydroxyteratin, etc., azo compounds, in particular, the nitrile group at the carbon atom, which is in c5i - to the atom of the azo group, for example, dimethyl and dehydrotyphosphate, and for example, dimethyl and nitrophysulfur; and -.-azobis-o1,} - dimethylvaleronitrile Other known initiators can also be used according to the invention.
    The heat of reaction can be removed by various known methods, for example, using gas flows, cooling through the wall and cooling elements installed in the reactor. Then, chlorination is practically carried out in the absence of moisture. It is especially advisable to remove the heat of reaction by evaporating water, liquid chlorine, or other inert liquids injected or sprayed into the reactor. It is preferable to use water as a coolant, which can also be added initially in an amount almost equal to the amount of polyethylene powder.
    Examples 1-6. 200 g of polyethylene powder was loaded into a horizontally located reactor with a capacity of 4 liters, an internal diameter of 13 cm, a wall thickness of 3 mm, equipped with internal protrusions about 0.5 cm high, inlet and outlet for gas and a thermocouple as baffle baffles 28.
    The thermocouple is connected to four 250-watt infrared heating lamps located outside the reactor, and an automatic recorder that records the temperature in the reactor. By means of a drive belt, the reactor is rotated at room temperature (about 22 ° C) by a motor at a constant speed of 40 rpm. Oxygen was displaced from the reactor by passing through it a stream of dry and pure nitrogen in the amount of 10 l / h for 30 min.
    Then the flow of nitrogen was replaced by a flow of dry hydrogen chloride (100 l / h), at the same time the heating system was turned on.
    During continuous passage of chlorine and rotation at a speed of 40 revolutions of the reactor, the contents were heated for 10 minutes from 22 to 125 ° C, after which the automatically controlled heater system maintained the temperature for 10 minutes 125t2c, and if necessary, the walls of the reactor were cooled with compressed air at a temperature of 20 ° WITH.
    The gases coming out of the reactor were passed through a 30% aqueous solution of a monohydrogen, while being absorbed
    unreacted chlorine and the resulting hydrogen chloride.
    The heating system was then turned off and the chlorine stream was replaced with a stream of nitrogen (100 l / h), which was fed for 1 hour to remove hydrogen chloride and unreacted chlorine from the polymer. The chlorinated polymer was quantitatively removed from the reactor, weighed (weight Q.), then sieved through a sieve with 1000 micron holes. Then it was determined the weight amount of the polymer, which could not pass through the sieve (weight e). Based on these data, the percentage of polymer sintering was calculated by the formula
    . % sintering f 100%.
    The following types of polyethylene were chlorinated this way.
    Polyethylene A. High density polyethylene having a melt index of 0.02 g / 10 min, particle size distribution from 100 to 600 µm, a porosity of 0.085 BET specific surface area of 0.5 and a melting point of crystallite. The wax content determined after 48-hour extraction from polyethylene powder by n-hexane in the extraction apparatus was up to 3% by weight. Density is 0,9468 g / cm.
    Polyethylene VG Hostal Höhst GM 7745 polyethylene powder, having a melt index of 0.11 g / 10 min, particle size distribution from 100 to boo m, porosity 0.04, BET specific surface area 0.1 mVr and melting point of crystallite 107 ° C. The wax content is 2.8% by weight.
    Polyethylene Cg Khostalen GF 7660 P also powdered polyethylene of the company Hoechst, having an index of length of 0.35 g / 10 min, granulometric composition from 100 to 600 µm, a porosity of 0.02 cMVr, a melting point of crystallite about 108 s and a wax content of 1.0% by weight.
    Polyethylene Dg as polyethylene B, but with a wax content by extraction with n-hexane to 0.8% by weight.
    Polyethylene E as polyethylene C, but with wax content up to 0% by extraction with n-gzxane.
    Polyethylene P Polyethylene powder, obtained by grinding stamilan tablets; 9800 (polyethylene D5M) having a melt index of 0.30 g / / 10 min, particle size distribution from 175 to 250 μm, porosity 0.038 cmVr, specific surface according to BET 0.1, wax content 0.1% by weight. Crystallite melting point and density 0.958 g / cm
    The results of chlorination, especially when sifting through a 1000 µm sieve, are listed in Table 1.
    Tablg-1 shows that powders of high-density polyethylene can be chlorinated in bulk without sintering or with very little sintering even at a temperature above the melting point of the crystallite, if the wax content in the powders is 1% by weight. At. higher wax content possible sintering.
    Examples 7-14 (comparative.).
    0
     Anslogical1: about examples 1-6, polyethylene powder was chlorinated, having an index of 11.30, particle size of more than 90% from 50 to 300 microns, i.e. 5% less microns
    5 and more than 300 µm, porosity of 0.243, BET specific surface area of 2.1, melt point of crystallite Allite ° C, wax content less than 0.1% by weight and density
    0 0.958 g / cm, and the temperature is mediocre from 25 to.
    The experiment set the temperature at which the effect of agglomeration and / or darkening has not yet begun. When the temperature was reached, the chlorine content was 17% by weight. Its content increased at lower heating rates. Then the temperature was raised within 3-4 minutes to 125 C and
    0 Chlorination was performed to different final chlorine contents. The content of chlorine and the elasticity of chlorinated polyethylene were determined. To determine the elasticity, homo5 genizable the chlorinated polyethylene powder with 1% by weight Irgastaba T9- (Irgastab T9 is sold by the company. Ciba-Geigy and consists mainly of dubityltin maleinate) on
    0 rolls, after which small bar samples were made for testing. These rods were tested for torsional Klach and Berg. The temperature was determined and the modulus of the k-trench was measured at 700 kg / cm, so-called.
    5, the value of Q is 700. This value of C 700 is a measure of elasticity: Ti of chlorinated polyethylene powder. At Q-700 values below 0 ° C, elasticity can be estimated as
    0
    excellent, at values & 700 higher elasticity should be considered insufficient.
    At the same time, the effectiveness of chlorinated poly5 ethylene powder as an agent for improving the impact strength of PVC was determined. For this purpose, 15 weight parts were homogenized on the rolls. this powder, 85 weight.h. Varlan 6600 (PVC type with a value of K 66 sold by D5M) and
    0 1 weight.h. Irgastaba T9.
    Small test plates were made from rolled sheets, impact strength was determined at 20 ° C and 0 ° C (according to ISODE).
    five
    The results are shown in table 2.
    From Table 2 it can be seen that chlorination in the mass of high-density polyethylene, having a large specific surface, results in chlorinated polyethylene having insufficient elasticity and low efficiency as an agent for improving the impact strength of PVC. .
    Examples 15-23. Similarly to examples 1-6, powders of polyethylene A and F were chlorinated to a different final chlorine content. However, the reactor and its contents were heated for 15 minutes from 22 to, and then chlorination was carried out at 140 + 2 s to varying degrees.
    Ki in one of the cases described above did not occur sintering
    (the percentage of sintering 0). The resulting end products were white, free flowing powders. Similarly to Examples 7-14, the chlorine content, the elasticity expressed in units, and the effectiveness as an agent for improving the impact strength of PVC (Izod at 20 and) were determined.
    The results are shown in table 3.
    From Table 3 it can be seen that chlorination in the mass of low-pressure polyethylene powders with a small specific surface area results in products with excellent elasticity and quality effectiveness; agent to improve the impact strength of PVC.
    a b and c a 1
    : gr
    ca.100 Coagulated3, 0
    2.8
    ca. 100 Same
    1.0
    OK. 3 Slightly small White Freedom 0.8 per weight, with charred parts of lumps with a radiant brown powder powder, having a non-refractory granulometric composition from 100 to 600 microns and a chlorine content of 12.8 wt.%
    There is no white free-flowing but flowable powder having a particle size distribution from 100 to 600 microns and a chlorine content of 14.5 wt.%.
    There is no white free-flowing but flowable powder having a particle size distribution from 100 to 600 μM and a chlorine content of 14.1 wt. %
    0.1
    32.4
    Continued table. one.
    no pecans. White free flowing powder, having a particle size range from 175 to 250 microns and a chlorine content of 15.1 wt.%.
    table 2
    LT. what about c 3
    12
    22
    权利要求:
    Claims (3)
    [1]
     ; Claim 14 A method for producing chlorinated polyethylene by chlorine treatment. Mass of micronized polyethylene of 15-160 ° G and 0-1-10 kg / cm 2-, characterized in that, in order to prevent sintering of polymer particles during chlorination, the initial a polymer containing 0-5 mol.% of C-Cg-Alkace links and having a density of 0.93 O / 97 g / cm, a melt index of 0.01-5, a porosity of 0.005-0.15 cm / g, specific surface area 0.1 -1 and wax content up to 1 wt.%. ,
    .
    [2]
    2 .. Method PO.P.1, about tl and h. Dts and so that the process is carried out
    The long table. 3
    successively in two stages: first, at a temperature below the floating point
    crystalline laziness - at 25-105С
    and
    then, at a temperature above the melting point of 20 crystallites of polyethylene at 110-150 ° C.
    [3]
    3. Method PO-PP.1 and 2, characterized in that during chlorination spraying is applied to the reaction mass, or water or liquid chlorine is sprayed.
    Sources of information taken into account in the examination
    1. Patent CMA 2890213, cl. 204-159.18, published 1959 ..
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    同族专利:
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    DE2806653A1|1978-08-17|
    ZA78730B|1979-01-31|
    BR7800912A|1978-10-10|
    AT363679B|1981-08-25|
    ATA90278A|1981-01-15|
    IN148047B|1980-10-04|
    NL7701599A|1978-08-18|
    FR2381069A1|1978-09-15|
    ES466900A1|1978-10-01|
    IT1102375B|1985-10-07|
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    IT7848043D0|1978-02-14|
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    DK70478A|1978-08-17|
    CA1098249A|1981-03-24|
    BE863924A|1978-08-14|
    IL53969D0|1978-04-30|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    BE552158A|1955-10-28|
    DE1720295B2|1967-08-29|1976-12-09|Basf Ag, 6700 Ludwigshafen|PROCESS FOR CHLORINATING POLYAETHYLENE|
    DE1720293A1|1967-08-29|1971-06-09|Basf Ag|Process for chlorinating polyethylene|
    NL7504616A|1975-04-18|1976-10-20|Stamicarbon|POST-CHLORINATED VINYL CHLORIDE POLYMERS.|
    US4029862A|1975-06-25|1977-06-14|The Dow Chemical Company|Olefin polymer chlorination products having improved handling properties and process for their preparation|DE3267981D1|1982-04-15|1986-01-30|Mitsui Petrochemical Ind|Chlorinated rubber and polyvinyl chloride composition containing the same|
    JPH0366325B2|1982-06-25|1991-10-17|Daisow Co Ltd|
    US4425206A|1982-12-09|1984-01-10|The Dow Chemical Company|Anhydrous process for preparing amorphous chlorinated polyethylene and product thereof|
    US4560731A|1983-07-15|1985-12-24|Union Carbide Corporation|Preparation of elastomeric, chlorosulfonated ethylene polymers|
    US4593075A|1983-07-15|1986-06-03|Union Carbide Corporation|Preparation of elastomeric, chlorinated ethylene polymers|
    JPH0533245B2|1984-11-08|1993-05-19|Mitsui Petrochemical Ind|
    EP0204816B1|1984-12-05|1991-11-06|The Dow Chemical Company|Halogenated ethylene polymers with improved resistance to agglomeration|
    JPH0367525B2|1985-03-13|1991-10-23|Nippon Sekyu Kk|
    CH663958A5|1985-03-14|1988-01-29|Dow Chemical Europ|METHOD FOR COATING PLASTIC OBJECTS.|
    US5068290A|1989-05-06|1991-11-26|Kang Hee Dong|Process for the chlorination of polyolefins|
    JPH0627131B2|1989-12-27|1994-04-13|日本製紙株式会社|Method for producing chlorinated polyolefin|
    US6124406A|1998-03-31|2000-09-26|The B. F. Goodrich Company|Blocky chlorinated polyolefins, process for making and use as impact modifier compatibilizer for PVC or CPVC|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NL7701599A|NL7701599A|1977-02-16|1977-02-16|METHOD FOR CHLORATING ETHENE POLYMERS.|
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