96results about How to "High hydrogen sensitivity" patented technology

The invention discloses a preparation method of polypropylene with high melt strength. The method includes i) a step of, under the action of a Ziegler-Natta catalyst containing a silane type external electron donor, subjecting propylene or propylene with other alpha-olefin to polymerization to obtain a polymer A having a melt mass flow rate of 0.01-0.4 g / min, with a hydrogen concentration being not more than 400 ppmV; ii) a step of adding a 1,3-diether type external electron donor and premixing the 1,3-diether type external electron donor and the polymer A; iii) a step of, under the existence of hydrogen and the premixed materials in the step ii), subjecting the propylene or the propylene with other alpha-olefin to polymerization to obtain a polymer B having a melt mass flow rate of 1.0-60 g / 10min; and a step of preparing polypropylene C with high melt strength comprising the polymer A and the polymer B. The melt mass flow rate of the polypropylene C is 0.8-15 g / 10min. The preparation method is simple and feasible and is convenient to operate and prone to industrial production. High-performance products with high melt strength and wide molecular weight distribution can be prepared by the method. The method has wide application prospect.

This invention provides a kind of magnesium halide adducts, whose general chemical formula is MgX2-mROH-nE-pH2O (I), wherein, X is Cl or Br; R is C1-C12 alkyl, C3-C10 cycloalkyl or C6-C10 aryl; E is dialkoxy hydrocarbon compound as shown in formula (II); m is 1-5; n is 0.005-1.0; p is 0-0.8. In formula (II), R1, R2, R3 and R4 are the same or different, and are H or C1-C10 linear or branched alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkylaryl or arylalkyl; two or more groups of R1 and R2 can bond into one or several fused rings; H is aryl or alkylaryl or H in benzene ring of arylalkyl can be substituted by halogen.

The invention provides an impact-resistant polypropylene material with high melt strength and a preparation method therefor. The polypropylene material comprises a propylene homopolymer component and a propylene-ethylene copolymer component; the molecular-weight distribution Mw / Mn of the material is smaller than or equal to 10 and is greater than or equal to 4; Mz+1 / Mw is greater than 10 and is smaller than 20; the room-temperature xylene soluble content of the material is higher than 10wt% and is lower than 30wt%; and the ratio of room-temperature trichlorobenzene soluble Mw to room-temperature trichlorobenzene insoluble Mw is greater than 0.4 and is smaller than 1. According to the method provided by the invention, a homopolymerized polypropylene continuous phase, which has a specific melt index and has extremely wide molecular weight distribution, is prepared through using external electron donors of different types and use levels and hydrogen gas of different use levels separately at different polymerization stages, then, propylene and ethylene copolymerization is further carried out so as to obtain a rubber phase, and then, the impact-resistant polypropylene material with high melt strength, high rigidity and high toughness is obtained.

The invention belongs to polyethylene catalysts, and particularly relates to a titanium fluoride modified load type chrome alum double-active center catalyst. The titanium fluoride modified load type chrome alum double-active center catalyst comprises an inorganic carrier and loaded active components and modified components. The active components comprise chromium oxides and vanadium oxides, and the modified components comprise fluorine and titanium. According to the catalyst, the content and distribution of comonomers are improved, the number of the comonomers inserted into a low molecular weight end is reduced, the number of the comonomers inserted into a high molecular weight end is increased, and therefore more chalaza molecules can be formed easily, and polyethylene products with better performance are prepared. Meanwhile, the catalyst has the advantages of being high in activity, sensitive in hydrogen regulation response performance and the like. The invention further provides a preparation method of the catalyst. The inorganic carrier is firstly loaded with one of the modified components, and then loaded with the rest of the components, the process is reasonable, and industrial production is easy.

The invention discloses a catalyst component used for an ethylene polymerization reaction, a preparation method thereof and a catalyst prepared therefrom. The catalyst component comprises a magnesium alcohol adduct, a titanium compound, acrylate and a derivative thereof, an organic aluminum compound, a monoester compound and a free radical initiator. The catalyst is high in mechanical strength and hydrogen regulation sensitivity and is not liable to break during polymerization. A prepared polyethylene powder material is high in stacking density, is very concentrated in particle size distribution and is less in contents of thick powder and fine powder.

The invention provides a preparation method of a catalyst solid component for olefin polymerization. The method comprises: (1) preparing a magnesium halide alcohol adduct solution, namely carrying out reaction on anhydrous magnesium halide, an alcohol compound, titanate and a first part internal electron donor in an alkane or aromatic solvent solution to obtain the magnesium halide alcohol adduct solution; and (2) preparing the catalyst solid component, namely enabling a second part internal electron donor to react with titanium halide and the magnesium halide alcohol adduct solution which is obtained in the step (1) so as to obtain the catalyst solid component, wherein the internal electron donors are the same and are ester compounds with structural formulas shown by the formula 1, and in the formula 1 which is shown in the specification, R1 and R2 are selected from hydrogen atoms, and alkyl groups and naphthenic bases with 1-8 carbon atoms, and R3 and R4 are selected from alkyl groups and naphthenic bases with 1-8 carbon atoms. According to the preparation method provided by the invention, the potential safety hazard of a plasticizing agent to a human body is eliminated, the finally polymerized product is high in isotacticity and high in performance, the cost is reduced, and the process is simple and is high in yield.

The invention relates to the field of olefin polymerization catalysts, and specifically relates to a solid catalyst component and catalyst system used for olefin polymerization, and an olefin polymerization method. The solid catalyst component includes reaction products of the following components: 1) a liquid component containing magnesium, 2) a titanium compound, 3) an internal electron donor compound, and optionally selected 4) an assistant precipitating agent. The internal electron donor compound is selected from at least one of cyclotriveratrylene and derivatives thereof shown as a formula (I), and M1-M6 are selected from hydrogen, hydroxy, amino, an aldehyde group, a carboxyl group, an acyl group, halogen atoms. Through the introduction of the cyclotriveratrylene and derivatives thereof as internal electron donors, the polymerization activity, hydrogen response and copolymerization performance of the polyolefin catalyst can be enhanced. The structure of the cyclotriveratrylene and the derivatives thereof is shown as the formula (1).

The invention provides a catalyst system for vinyl polymerization. The catalyst system for the vinyl polymerization is prepared from the following components: a component A: a titanium-containing solid catalyst component, a component B: an organic aluminum compound, a component C: a halogenated naphthene compound, and a compound D: a halogenated metal compound, wherein a preparation method of the component A comprises the steps of dissolving magnesium halide into a solvent system containing an organic alcohol compound so as to form a solution, adding a reactive hydrogen-free organic silicon compound into the solution to obtain a mixed solution, then enabling the mixed solution to react with a titanium compound by contacting for carrying out a titanium loading process, optionally adding or not adding the reactive hydrogen-free organic silicon compound and carrying out reaction, stirring, and then washing. When being used for the vinyl polymerization, the catalyst system provided by the invention is not only higher in catalytic activity, but also is higher in hydrogen sensitivity, thus being suitable for producing polyethylene with wide molecular weight distribution and high melt index.

The invention provides an olefin polymerization catalyst, as well as a combined catalyst containing the same and an application thereof. The olefin polymerization catalyst contains reaction products of the following raw materials: a composite carrier prepared by spray-drying magnesium halide and silicon dioxide, at least one compound selected from a group composed of dihydric alcohol sulphonate compounds, at least one compound selected from a group composed of a monohydric fatty group carboxylic ester compound, a dihydric fatty group carboxylic ester compound, a monohydric aromatic carboxylic ester compound, a dihydric aromatic carboxylic ester compound and a diether compound, and a titanium halide compound. The combined catalyst contains the olefin polymerization catalyst, an alkyl aluminium compound and the like. The olefin polymerization catalyst adopts two kinds of internal electron donor compounds, and can guarantee the stereoregularity of a prepared polymer while guaranteeing the catalyst activity.

The invention provides a carrier for an ethylene polymerization catalyst and a catalyst of the carrier. The carrier comprises reactants of the following components: magnesium chloride / gallic acid derivatives / epoxy compounds with carbon-carbon double bonds / alcohol compounds / radical initiators. A mixed solution of the components is initiated by the radical initiators in the process of warming, and the carbon-carbon double bonds in a system can generate a polyreaction, so that the carrier with narrow particle size distribution and doped with polymers can be separated out. The polyethylene catalyst prepared through the carrier not only has the characteristic of narrow particle size distribution but also is high in hydrogen adjustment sensibility; the particle size distribution of obtained polymeric powder materials is particularly intensive, and less fine powder is generated.

The present invention relates to a high hydrogen response olefin polymerization catalyst component and a preparation method thereof, and an olefin polymerization method. According to the present invention, an organic silane compound and a diether internal electron donor compound are simultaneously introduced during a catalyst component preparation process, and the prepared catalyst component is used for polymerization, particularly for propylene polymerization, such that the hydrogen regulation performance of the catalyst system is increased, the particle morphology of the polymer is improved, and the original isotacticity and other high excellent performances of the catalyst system can be well maintained. In addition, the method of the present invention is suitable for a slurry polymerization method, a bulk polymerization method, a gas phase method, and a plurality of polymerization processes.

The invention relates to a carrier used for an olefin polymerization catalyst and a preparation method thereof. The carrier is (MgXY)m.[Mg(OR')Z]p.(ROH)n. The preparation method comprises the following steps: mixing magnesium halide as shown in MgXY, a compound as shown in ROH and a first inert medium; carrying out heating at 90 to 150 DEG C for 0.5 to 5 h; then emulsifying a liquid-state mixture obtained in the previous step; introducing an emulsification product to a second inert medium which has been cooled to -40 to 10 DEG C for rapid cooling and forming; carrying out solid-liquid separation so as to obtain a spherical carrier; and carrying out washing and drying so as to obtain the carrier. According to the invention, a forming agent and a grain-shape controlling agent are added during formation of an alcohol adduct of magnesium halide, so the obtained carrier has more concentrated particle size distribution; the catalyst prepared from the carrier has improved activity and hydrogen sensitivity when applied to olefin polymerization, especially to propylene polymerization; and an obtained polymerization product has moderate bulk density and is almost free of special-shaped materials.

The invention discloses a loaded olefin polymerization solid catalyst ingredient, comprising a composite carrier SiO2 and a magnesium-containing compound of ClMg(OR)-n(ROH), and pyridine-2-alkyl imine titanium tetrachloride of formula (I) and TiCl4, wherein in the ClMg(OR)-n(ROH), R is selected from C1-C4 alkyl, n ranges from 0.1-1.0; in the formula (I), R1 and R2 are respectively monosubstituents or polysubstituents on pyridine ring and aniline ring and respectively selected from hydrogen, C1-C6 alkyl, phenyl or C7-C8 aralkyl, R3 is selected from hydrogen or C1-C3 alkyl, and the catalyst comprises 1.0-8.0 wt% of magnesium, 0.2-5.0 wt% of titanium, 0.1-0.9 wt% of nitrogen, and 40-80 wt% of SoO2. The catalyst used in olefin polymerization has good hydrogen response, and the obtained polymer has good form and bulk density and high melt index.

The invention provides an external donor compound. Aluminium alkyl is introduced into a compound with calixarene group and organosilicon amino group; when used as an external donor compound of olefin polymerization catalyst with a main catalyst of Ziegler-Natta type catalyst, the compound can endow the olefin polymerization catalyst with high stereoselectivity and hydrogen response, so as to actively prepare a polymer with high fusion index and high isotacticity and a polymer with low fusion index and high isotacticity.

The present invention discloses a catalyst component used for olefin polymerization and a preparation method thereof, a catalyst used for the olefin polymerization, which contains the catalyst component, and application of the catalyst used for the olefin polymerization in the olefin polymerization. The catalyst component comprises the following reaction products: 1, a magnesium-containing carrier; 2, at least one titanium compound; and 3, at least one internal electron donor, wherein the magnesium-containing carrier is a product obtained by reaction of a compound shown as a formula (1) and an oxirane compound shown as a formula (2). When the catalyst component prepared by the carrier is used for olefin (particularly propylene) polymerization, bulk density of a polymerization product can be reduced, hydrogen regulation sensitivity of the catalyst is improved, and the polymerization product is substantially free of heterogeneous materials. The formula (1) is shown as MgXY.(ROH)p.(H2O)q, and the formula (2) is as shown in the specification.

The invention discloses a catalyst component for olefin polymerization. The catalyst component contains titanium, magnesium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises an amino ester compound shown as general formula I in the description. A catalyst with excellent combination property can be obtained by adopting a novel internal electrondonor system, satisfactory polymerization yield can be realized when the catalyst is applied to propylene polymerization, hydrogen response of the catalyst is improved, the stereospecificity is higher, and development of polymers with different grades is facilitated.

The invention relates to a catalyst for ethylene polymerization. The catalyst comprises: A. a titanium-containing solid catalyst component, which is obtained by: dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound, then adding an electron donor compound to form a uniform solution, in the presence of an assistant precipitation agent, mixing the solution with a halide of titanium or its derivative, and conducting washing and drying to obtain a solid a; reacting a silicon compound with the solid a in an inert solvent, and performing washing and drying; and B. an organic aluminum compound with a general formula of AlRnX3-n, wherein n is alkyl with a hydrogen or carbon atom number of 1-20, X is an halogen atom, and n is an integer larger than 0 and smaller than or equal to 3. The catalyst component can have high catalyst activity and high hydrogen regulation sensitivity when it is applied to ethylene polymerization, and the obtained polymer can have a low fine powder content. The catalyst is suitable for slurry polymerization or gaseous polymerization of ethylene, and is especially suitable for an ethylene gaseous fluidized bed polymerization process with the catalyst fed in a slurry form.

The invention provides a solid catalyst component for an olefin polymerization reaction. The solid catalyst component comprises magnesium, titanium, halogen and an electron donor. The electron donor is at least one of diol ester compounds shown in the general formula (I). The catalyst provided by the invention has greatly improved polymerization activity, hydrogen response and stereospecificity. Through the solid catalyst component and the catalyst, a polymer having a high fusion index and high isotacticity is obtained. Compared with the prior art, the solid catalyst component has the advantages that if polymer melt indexes are the same, in other words, hydrogen response is the same, isotactic indexes are improved, and if polymer isotactic indexes are the same, the polymer melt indexes are improved, in other words, the hydrogen response is improved.

The invention relates to a catalyst composition used in an olefin polymerization reaction. The catalyst composition includes a solid catalyst component A, aluminum alkyl B and an external electron donor halogen-free malonate C, wherein the solid catalyst component A includes at least one of magnesium, titanium, a halogen and an internal electron donor containing lone pair electrons, such as a dialcohol ester compound (I); and the external electron donor C is a halogen-free malonate compound represented as the general formula (II). When the olefin polymerization reaction is carried out with the solid catalyst component A in the presence of the external electron donor C, the solid catalyst component A is very high in activity and especially is greatly enhanced in hydrogen-regulation sensitivity. In addition, some molecular weight distributions of the catalyst become wider and the external electron donor has a high-temperature self-quenching function.

The invention relates to an F-P interference type multipoint measurement hydrogen sensor based on an FBG interrogator. The F-P interference type multipoint measurement hydrogen sensor based on the FBGinterrogator comprises the FBG interrogator, a long-distance single-mode transmission optical fiber, an arrayed waveguide grating, an FP sensing head and a PC; the FP sensing head is composed of a hollow optical fiber, a PDMS (polydimethylsiloxane) thin film and a Pt / WO3 (platinum-loaded tungsten trioxide ) hydrogen-sensitive material; when hydrogen concentration is increased, the Pt / WO3 hydrogen-sensitive material reacts with hydrogen to release heat, volume of the PDMS thin film is expanded, length of an air-filled cavity is reduced, an interference spectrum of the FP sensing head can drift, then reflected light intensity of the arrayed waveguide grating is changed, and measurement on the hydrogen concentration can be realized by detecting change of the reflected light intensity by virtue of the PC. The F-P interference type multipoint measurement hydrogen sensor provided by the invention is simple in structure and high in sensitivity and can measure multiple points at the same time.

The invention provides a supported catalyst used for ethylene polymerization, and a composition and a preparation method thereof. The catalyst is composed of a component A, a component B and a component C, wherein the component A is prepared through the following steps: dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound and an electron donor compound to form a uniform solution, slowly reacting TiCl4 with the above obtained uniform magnesium halide solution at a low temperature to precipitate catalyst crystals, and carrying out a strictly controlled heating reaction; the component B is an organic aluminum compound; and the component C is a halogenated cycloalkane compound, and the component C can be used in anyone of the following three modes: (1) the component C and the component B are mixed, and the obtained mixture is added to an ethylene polymerization reaction system; (2) the component A, the component B and the component C are respectively added in the polymerization reaction; and (3) the component C is added in the preparation process of the component A. The catalyst has high catalytic activity and improved hydrogen sensitivity in ethylene polymerization.

The invention relates to a propylene polymer and a preparation method thereof. The MW of the polymer is 1.6-3.1*10<5>. The MW / Mn of the polymer is 3-15. The isotactic index of the polymer is 96.2-99.5%. The melt flow rate and the isotactic index satisfy the following formula: 101.0-1.1ln(x)-0.5<=y<=101.0-1.1ln(x)+0.5, wherein the y is the isotactic index and the x is the melt flow rate measured according to ASTM D1238-99 with the unit of g / 10min. The isotactic index of the propylene polymer provided by the invention is higher than that of polypropylene in the prior art with the same melt index as the propylene polymer provided by the invention.

The invention relates to a catalyst ingredient used for ethylene polymerization or copolymerization. The catalyst ingredient is characterized in that: the catalyst ingredient is obtained via loading a magnesium / titanium-containing solid material with at least one inorganic titanium compound, at least one organic titanium compound, at least one electron donor compound, and at least one activator. The magnesium / titanium-containing solid material is prepared by following steps: a magnesium compound is dissolved in a solvent system containing an alcohol compound, an organic epoxy compound, and an organic phosphorous compound so as to obtain a uniform solution; a halide of transition metal titanium or a derivative thereof is added for mixing; and the magnesium / titanium-containing solid material is obtained via precipitation in the presence of a precipitation accessory ingredient mixture. The magnesium / titanium-containing solid material is selected as a carrier, so that when the catalyst ingredient is used for ethylene polymerization, catalyst activity and hydrogen response are relatively high; an obtained polymer is low in fine powder content; the catalyst ingredient is suitable for ethylene slurry polymerization or gas phase polymerization, and is especially suitable for ethylene gas phase fluidized bed polymerization technology in which the catalyst is charged in a slurry form.

The invention relates to a propylene polymer production method which comprises the following steps: i) prepolymerization, namely prepolymerizing propylene in the presence of a catalyst to obtain a propylene prepolymer; and ii) polymerization in multiple temperature zones, namely introducing the propylene prepolymer obtained in step i) and propylene (or alpha-olefin containing propylene) together into one polymerization reactor or more polymerization reactors connected in series, introducing hydrogen into the polymerization reactor(s), and performing propylene homopolymerization or propylene and alpha-olefin copolymerization to obtain a propylene polymer. At least two continuous reaction zones exist, different reaction zones have different reaction temperatures, and the reaction temperatures are selected from 50-150 DEG C and preferably selected from 60-130 DEG C; and at least one high-temperature reaction zone exists among the reaction zones, and the reaction temperature of the high-temperature reaction zone is selected from 70-150 DEG C and preferably selected from 80-130 DEG C.

The invention relates to an olefin polymerization method. The method comprises steps as follows: a hexane solution of triethyl aluminum, a hexane solution of cyclohexyldimethoxymethylsilane and a catalyst are sequentially added to a high-pressure reactor under the protection of nitrogen, the high-pressure reactor is closed, 1.5-8.0 L of hydrogen and liquid olefin are added, the components are heated to 60-80 DEG C to react for 1-2 h, cooled, subjected to pressure release, discharged and dried, and polymers are obtained. According to the olefin polymerization method, a supporter and the catalyst are improved, so that when the catalyst prepared from the supporter is used for polymerization of olefin, especially, polymerization of propylene, activity and hydrogen regulation sensitivity of the catalyst can be improved, particle morphology of obtained polymers is good, bulk density of the polymers can be reduced, and no special-shaped materials are produced basically.

The invention provides a catalyst component for vinyl polymerization. The catalyst component comprises Ti, Mg, halogens and 1-99% of olefin polymers. The catalyst component for vinyl polymerization not only has the characteristics of high activity, high bulk density, low breaking rate of polymeric particles and low fine powder content, but also has good hydrogen regulating performance.

The invention discloses a method for preparing a solid catalyst component for an olefin polymerization reaction. The method comprises the following steps of dissolving a magnesium compound in a solvent system containing a hydrocarbon compound and an alcohol compound, mixing a titanium compound and the above solution at a temperature of -40 to 0 DEG C, adding an electron donor compound into the mixture at a temperature of 50-150 DEG C, and carrying out washing by an inert diluent to obtain the solid catalyst component. The used electron donor is at least one of diol ester compounds shown in the general formula (I). The catalyst system provided by the invention has greatly improved polymerization activity, hydrogen response and stereospecificity. Through the solid catalyst component and the catalyst, a polymer having a high fusion index and high isotacticity is obtained. Compared with the prior art, the solid catalyst component has the advantages that if polymer melt indexes are the same, in other words, hydrogen response is the same, isotactic indexes are improved, and if polymer isotactic indexes are the same, the polymer melt indexes are improved, in other words, the hydrogen response is improved.