CN103910929A

CN103910929A - Clay-enhanced polypropylene intra-autoclave alloy, preparation method for same, and applications thereof

Info

Publication number: CN103910929A
Application number: CN201310007846.3A
Authority: CN
Inventors: 董金勇; 秦亚伟; 王宁
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2012-12-31
Filing date: 2013-01-09
Publication date: 2014-07-09

Abstract

Disclosed are a clay-enhanced polypropylene intra-autoclave alloy, a preparation method for same, and applications thereof. The intra-autoclave alloy comprises a clay, a homopolymer polypropylene resin, and an olefin polymer. The preparation method is completed by utilizing a catalyst-polymer particle form-copying effect for in situ catalysis of a homopolymerization of propylene monomers and a polymerization reaction of one or two or more types of olefin monomers on a clay-loaded transitional metal catalyst that is spherical in terms of particle superficial form. The nanometer clay-enhanced polypropylene and copolymer resin prepared with the method are spherical in terms of particle forms; this not only implements the goals that the polymer is non-stick to an autoclave, flows easily, and is easy to transport, but also allows clay platelets in an exfoliated form to be distributed evenly in a resin substrate. The clay-enhanced polypropylene intra-autoclave alloy resin provided in the present invention has broad application prospects in the fields of automobile spare parts, packaging materials, barrier materials, flame retardant materials, electrical materials, construction materials, and materials for daily use products.

Description

Alloy And Preparation Method and application in the polypropylene that clay strengthens

Technical field

The present invention relates to the interior Alloy And Preparation Method of polypropylene and application that a kind of clay strengthens.

Background technology

Clay be a class cheap and easy to get, by nanoscale twins by the natural mineral matter of Van der Waals force combination, because of its can be under less addition (general addition is 3～5%) rigidity, resistance toheat and barrier property that can improve significantly polymkeric substance become one of the study hotspot in polymer nanometer modified field in recent years.

Polypropylene is also the macromolecular material that a class is cheap, cost performance is outstanding.In recent years, along with polyacrylic Application Areas is constantly widened, people have expressed higher requirement to its performance, expect that it can have the performance of just high and high-ductility concurrently.Be nano modifier and polypropylene alloy resin compounded by clay, become one of the most effective approach that realizes above-mentioned target.The method can be utilized the rigidity of clay, also can give full play to the toughness of rubber phase in polypropylene alloy, finally prepares the polypropylene alloy resin of rigidity-toughness balanced.Wherein, the composite nanometer-level polypropylene/montmorillonoid material of preparing with blending method has demonstrated huge application potential in automobile plastic.

In-situ polymerization is considered to prepare one of the most effective method of nanometer composite polypropylene material.This technology is the catalytic active center catalyzing propone monomer polymerization reactions by being enriched in the polyolefine transition catalyzer between clay layer, avoid by polypropylene and polynite polarity difference and the thermodynamic (al) harsh requirement causing, and then successfully prepared nanometer Reinforced Polypropylene resin.(CN1824696A, US6613711B2, CN101235169A, US6465543131, US5830820) simultaneously, in-situ polymerization technology allows, in recombination process, polypropylene matrix is carried out to molecular designing, therefore not only can be by changing polyolefin catalyst or copolymerization flexible polypropylene composition and structure, obtain the different nano composite material of matrix properties, expand performance range, can also can cause forming the interactional functional groups of strong interface with clay layer by introducing on polypropylene matrix, thereby interface is designed, effectively embody nano combined nano effect (the Huang Y J that Properties of Polypropylene is improved, Yang K F, Dong J Y.Macromol RapidCommun, 2006, 27:1278-1283).Also the angle that has investigator to prepare from catalyzed polymerization and scale, the clay loaded polyolefin catalyst from preparation with spherical morphology is started with, successfully solve the poor problem of particle form in the in-situ polymerization preparation process of polypropylene nano compound resin, and particle reaction device technology is incorporated into the preparation process of polypropylene nano compound resin, successfully prepare alloy in the polypropylene that nanometer strengthens.(Qin?YW，Wang?N，ZhouY，Huang?Y?J，Niu?H，Dong?J?Y.Macromol?Rapid?Commun2011，32：1052-1059)

Use clay loaded polyolefin catalyst, the equal polyreaction of segmentation catalyzing propone and one or more olefinic monomer polyreactions, have no report.

Summary of the invention

The object of this invention is to provide Alloy And Preparation Method and application in a kind of clay Reinforced Polypropylene still.

Alloy in the polypropylene that clay provided by the invention strengthens, comprises clay, homo-polypropylene resin and olefin polymer.

In the polypropylene that this clay strengthens, alloy also can only be made up of said components.

Described homo-polypropylene resin is selected from least one in isotatic polypropylene, syndiotactic polypropylene and Atactic Polypropelene resin; The weight-average molecular weight of described homo-polypropylene resin is 20000-1000000g/mol, is specially 200000-800000g/mol;

Described olefin polymer is the polymkeric substance being obtained by one or both monomer polymerization reaction take places in alpha-olefin, and described olefin polymer is not homo-polypropylene; Wherein, described alpha-olefin is ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-nonene or 1-decene; Concrete, described olefin polymer is the poly-1-octene of homopolymerization isotactic, ethene/1-octene random copolymers, propylene/1-butene random copolymer, propylene/1-butene random copolymer, homopolymerization isotactic poly-1-butylene, homopolymerisation polyethylene or ethylene/propylene olefinic random copolymer;

The mass ratio of described homo-polypropylene resin and described olefin polymer is 40.0～99.0: 1.0～60.0, is specially 60-95.5: 4.5-40; Be more specifically 88.46: 10.2 or 86.08: 13.1 or 74.24: 25.2 or 93.81: 5.55 or 86.83: 5.55 or 77.05: 22.5 or 92.98: 5.6 or 95.5: 2.5 or 74.24-95.5: 5.55-25.2 or 77.05-93.81: 5.55-22.5;

The quality percentage composition that described clay accounts for the interior alloy of polypropylene of described clay enhancing is 0.01-25%, being specially 0.2-5%, is more specifically 1.34% or 0.82% or 0.56% or 0.64% or 0.67% or 0.45% or 1.42% or 2% or 0.45-2% or 0.56-1.42% or 0.64-1.34%.

In the polypropylene that described clay strengthens, the particle mode of appearance of alloy is spherical, and particle diameter is 10～10000 μ m, is specially 50-1000 μ m, is more specifically 50～200 μ m or 50～500 μ m;

Described clay exists with the sheet form of peeling off in alloy in described polypropylene.

In the polypropylene that above-mentioned clay strengthens, alloy also can be the product of preparing by the following method and obtain.

In the polypropylene that the above-mentioned clay of preparation provided by the invention strengthens, the method for alloy, comprises the steps:

1) in inert atmosphere, propylene monomer and clay load transition metal catalyst and promotor are carried out to slurry polymerization in organic solvent, react the complete mixture that contains clay and homo-polypropylene resin of obtaining;

Or, propylene monomer and clay load transition metal catalyst, promotor are carried out to bulk polymerization, react the complete mixture that contains clay and homo-polypropylene resin of obtaining;

2) in inert atmosphere, to described step 1) gained contain clay and homo-polypropylene resin mixture in add one or both alpha-olefins, in organic solvent, carry out slurry polymerization, react the complete interior alloy of polypropylene that described clay strengthens that obtains;

Or, to described step 1) gained contain clay and homo-polypropylene resin mixture in add one or both alpha-olefins to carry out polyreaction, react complete obtain clay strengthen polypropylene in alloy.

In the method, described promotor is selected from least one in the aluminum alkyls of C1-C4 and the aluminum alkoxide of C1-C4, is specifically selected from least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and methylaluminoxane;

Described step 1) and 2) in, described organic solvent is all selected from least one in the alkane of C5～C10 and the aromatic hydrocarbon of C6-C8, is specifically selected from least one in heptane, hexane and toluene; Or,

Described alhpa olefin is ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-nonene or 1-decene.Described step 1) in, in aluminium element in promotor and clay load transition metal catalyst, the mol ratio of transition metal is 1～5000: 1, be specially 10-2000: 1, be more specifically 200: 1 or 400: 1 or 600: 1 or 2000: 1 or 200-2000: 1 or 200-600: 1 or 200-400: 1 or 400-2000: 1 or 400-600: 1 or 600-2000: 1 or 400-600: 1;

The add-on of described clay load transition metal catalyst is the 0.1-20% of described propylene monomer quality, is specially 0.4-10%, is more specifically 0.4% or 1.25% or 0.4%-1.25%;

Described step 2) in, the add-on of described alpha-olefin is 0.5～80.0% of the described step 1 gained mixture quality that contains clay and homo-polypropylene resin, being specially 1-80%, is more specifically 33% or 77% or 38% or 20% or 56% or 60% or 63% or 42% or 31% or 20%-77% or 31%-63% or 33%-60% or 38%-42% or 20-56%;

While selecting two kinds of alhpa olefins, the additional proportion of two kinds of alhpa olefins is arbitrary proportion, is specially propylene and 1-butylene that mass ratio is 5-20: 40-80, or mass ratio is ethene and the propylene of 5-20: 40-80, or mol ratio be 1: 2 ethene and propylene;

Described method also comprises the steps: in described step 1) before slurry polymerization or bulk polymerization, be R to adding general structure in reaction system _4-nsi (OR ') _nexternal electron donor;

Described R _4-nsi (OR ') _nin, the integer that n is 1-3, R and R ' are all selected from least one in alkyl, the cycloalkyl of C5-C10 and the aryl of C6-C10 of C1-C8, are specifically selected from least one in alkyl and the phenyl of C1-C5, and more specifically, R is methyl, and R ' is phenyl, and n is 2; Described external electron donor is specially dimethyl diphenyl silane; In external electron donor and promotor, the mol ratio of aluminium element is 0.01-1.0: 1, and concrete 0.1-1.0: 1;

Described method also comprises the steps: in described step 1) before slurry polymerization or bulk polymerization, in reaction system, pass into hydrogen; Wherein, the add-on of described hydrogen is the 0-0.5% of described propylene monomer quality, is specially 0-0.1%, be more specifically 0.02% or 0.04% or 0.08% or 0.02-0.08% or 0.02-0.04% or 0.04-0.08%, and the add-on of described hydrogen is not 0;

Described method also comprises the steps: in described step 2) before slurry polymerization or polyreaction, in reaction system, pass into hydrogen; Wherein, the add-on of described hydrogen is the 0-5.0% of described alhpa olefin gross weight, be specially 0-0.5%, be more specifically 0.035% or 0.04% or 0.05% or or 0.0625% or or 0.067% or 0.07% or 0.1% or 0.15% or 0.04-0.15% or 0.05-0.1% or 0.04-0.07% or 0.04-0.067% or 0.035-0.07%, and the add-on of described hydrogen is not 0.

Described step 1) in, the temperature of described slurry polymerization and bulk polymerization is 30 ℃～90 ℃, be specially 70 ℃ or 75 ℃ or 70-75 ℃, time is 0.05～10.0 hour, be specially 0.2 hour or 0.5 hour or 0.2-0.5 hour, pressure is 0-4MPa, is specially 0.5-3.5MPa, described pressure is not 0, is more specifically 0.70MPa or 3.10MPa or 3.00MPa or 3.2MPa or 0.70-3.10MPa or 0.70-3.00MPa or 3.00-3.10MPa or 0.7-3.2MPa;

Described step 2) in, the temperature of described slurry polymerization and polyreaction is 50 ℃～120 ℃, be specially 50 ℃ or 70 ℃ or 90 ℃ or 50-90 ℃ or 70-90 ℃ or 50-70 ℃, time is 0.1～10.0 hour, is specially 0.2 hour or 0.5 hour or 1 hour or 2 hours or 0.2-2 hour or 0.5-1 hour or 0.2-0.5 hour or 0.5-2 hour or 0.2-1 hour or 1-2 hour; Pressure is 0-4MPa, be specially 0.5-3.5MPa, described pressure is not 0, is more specifically 0.50MPa or 1.00MPa or 1.2MPa or 2.50MPa or 1.70MPa or 0.50-2.50MPa or 1.00-1.70MPa or 0.50-1.70MPa or 0.50-1.00MPa or 1.00-2.50MPa or 1.70-2.50MPa;

In addition, in aforesaid method, clay load transition metal catalyst used is disclosed clay load transition metal catalyst in the Chinese invention patent application that application number is 200910235506.X.This clay load transition metal catalyst is made up of clay catalyst carrier, transistion metal compound, metallic compound and internal electron donor; Its particle mode of appearance is spherical, and particle diameter is 5-100 micron, and specific surface area is 5-500m ²/ g, mean pore size is 2-50 nanometer, pore volume is 0.05-100cm ³/ g;

Wherein, described clay catalyst carrier is made up of clay mineral and reactive silicon dioxide;

Described reactive silicon dioxide, to be prepared according to the method that comprises following steps: silicon ester or silicon ester sodium and silicon-containing organic compound with reactive group are issued to unboiled water solution and condensation reaction take mol ratio 1: 0.01-0.5, temperature of reaction as the condition of 0-80 ℃, react and obtain described reactive silicon dioxide after 0.5～20.0 hour; Or, silicon ester is mixed with alkaline reactive medium, be to carry out solgel reaction under the condition of 0-80 ℃ in temperature of reaction, react and obtain described reactive silicon dioxide after 0.5～20.0 hour;

Wherein, the general structure of described silicon ester is Si (OR) ₄, R is straight chain or the isomerized alkyl that the total carbon atom number of main chain and side chain is 1～18;

The general structure of the described silicon-containing organic compound with reactive group is R ' _msi (OR) _n, R ' is selected from hydroxyl, alkoxyl group, carboxyl, epoxy group(ing), two key, amino, sulfydryl, urea groups, four sulfenyls and halogen, 1≤m≤3, and 1≤n≤3, R is straight chain or the isomerized alkyl that the total carbon atom number of main chain and side chain is 1～18.In the reaction medium that described hydrolysis and condensation reaction and solgel reaction are is 8～11 in pH value, carry out, it is at least one in 2 to 12 monohydroxy-alcohol, acetone and water that described reaction medium is selected from tetrahydrofuran (THF), carbonatoms.

In described clay catalyst carrier, described clay mineral is selected from polynite, mica, vermiculite and at least one in the clay mineral of organic intercalation agent modification; Wherein, described in the clay mineral of organic intercalation agent modification, described organic intercalation agent is selected from at least one in the alkyl quaternary ammonium salts of two keys, hydroxyl, amino or alkoxyl group, imidazole salts and alkyl microcosmic salt; In the described alkyl quaternary ammonium salts with two keys, hydroxyl, amino or alkoxyl group and alkyl microcosmic salt, the general structure of described alkyl is CH ₃(CH ₂) n-, 6≤n≤10000, are specially 12-18;

The described clay mineral through organic intercalation agent modification, to be prepared according to the method comprising the steps: the clay mineral of 0.01～0.1 mass parts is scattered in to the water of 1 mass parts or is to form suspension in the mixed solution that forms of 0.05～3: 1 alcohol and water by volume ratio, adding mole dosage is clay mineral 0.5-20 organic intercalation agent doubly again, at 20～90 ℃, react after 4.0～20.0 hours and filter, the mixed solution washing of water or alcohol and water, vacuum-drying 4.0～24.0 hours at 60～100 ℃ again, obtain the described clay mineral through organic intercalation agent modification,

Wherein, described alcohol is selected from least one in methyl alcohol, ethanol, n-propyl alcohol and Virahol; The mole number of described clay mineral is by cation exchange capacity;

The mass ratio of described clay mineral and described reactive silicon dioxide is 80-99.5: 0.5-20;

In described clay mineral, cation exchange capacity is 80-120meq/100g, and specific surface area is 10-700m ²/ g, mean pore size is 5-50 nanometer, pore volume is 0.05-500cm ³/ g, sheet interlayer spacing is 1.0-5.0 nanometer, the positively charged ion adsorbing in described clay mineral is Na ⁺, K ⁺, Ca ²⁺, H ⁺or Li ⁺;

The median size of described reactive silicon dioxide is 5-100 nanometer;

The particle mode of appearance of described clay catalyst carrier is spherical, size 5-100 micron, and specific surface area is 10-700m ²/ g, mean pore size is 5-50 nanometer, pore volume is 0.05-500cm ³/ g;

Described transistion metal compound is selected from least one in Ziegler-Natta catalyst, metallocene catalyst and non-metallocene catalyst;

Wherein, described Ziegler-Natta catalyst titanium tetrahalide used is TiCl ₄, TiBr ₄or TiI ₄;

Described metallocene catalyst is suc as formula shown in II general structure,

(Cp ^I-B-Cp ^II)MR ¹ _aR ² _b

Formula II

In described formula II, M is selected from least one in Ti, Zr, Hf, V, Fe, Y, Sc and lanthanide series metal;

Cp ⁱand Cp ^iIall represent cyclopentadienyl or contain substituent cyclopentadienyl; Described containing in substituent cyclopentadienyl, substituting group is selected from C ₁～C ₆alkyl, C ₃～C ₁₈cycloalkyl and C ₆～C ₁₈aromatic base at least one;

R ¹and R ²at least one in the silylation of the aryl of the C6～C20 replacing for the alkyl of the aryl of the alkoxyl group of the alkyl of H, halogen atom, C1～C8, C1～C8, C6～C20, C1～C15, acyloxy, allyl group and the C1～C15 of C1～C8;

A and b are the integer of 0-2, and a+b=2;

Described B represents alkyl bridge or silylation bridge, be specially-C (R ³r ⁴)-or-Si (R ³r ⁴)-; Described-C (R ³r ⁴)-or-Si (R ³r ⁴)-in, R ³and R ⁴be the alkyl of H, C1～C4 or the aryl of C6～C10; E is 1,2 or 3;

Described metallocene catalyst is specially C ₂h ₄(Ind) ₂zrCl ₂, C ₂h ₄(H ₄ind) ₂zrCl ₂, Me ₂si (Ind) ₂zrCl ₂, Me ₂si (2-Me-4-Ph-Ind) ₂zrCl ₂, Me ₂si (Me ₄cp) ₂zrCl ₂, Me ₂si (Flu) ₂zrCl ₂, Me ₂si (2-Me-4-Naph-Ind) ₂zrCl ₂or Ph ₂si (Ind) ₂zrCl ₂; Wherein, Me is methyl, and Ph is phenyl, and Cp is cyclopentadienyl, and Ind is indenyl, H ₄ind is 4,5,6,7-tetrahydro-indenes, and Flu is fluorenyl, and Naph is naphthyl;

Described non-metallocene catalyst as shown in formula III general structure,

formula III

In described formula III, M is selected from least one in Zr, Ti, V and Hf;

R ¹, R ²and R ³all be selected from least one in the silylation of acyloxy, allyl group and C1～C15 of aryl, the C1～C8 of C6～C20 that the aromatic base of aryl, the C6～C18 of the C6～C20 of the cycloalkyl substituted of aryl, the C3～C18 of C6～C20 that the alkyl of aryl, the C1～C6 of alkoxyl group, the C6～C20 of alkyl, the C1～C8 of H, halogen atom, C1～C8 replaces replaces; X is halogen atom, Cl, Br, I or F; N is 2;

Described non-metallocene catalyst is specially two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride, two [N-(3-methyl salicylidene) anilino] zirconium dichloride, two [N-(3-sec.-propyl salicylidene) anilino] zirconium dichloride or two [N-(3-adamantyl-5-methyl salicylidene) anilino] zirconium dichloride;

Described metallic compound is magnesium-containing compound and/or aluminum contained compound;

Wherein, described magnesium-containing compound is that molecular formula is MgX ₂magnesium halide or the general structure Grignard reagent that is RMgX; Described MgX ₂in, X is fluorine, chlorine, bromine or iodine element; In described RMgX, R is that carbonatoms is the alkyl of 1-10, and X is fluorine, chlorine, bromine or iodine;

Described aluminum contained compound is Al (OR ') _nr _3-n, the integer that n is 0-3, R and R ' are the alkyl of C2～C10;

Described internal electron donor is selected from least one in diisobutyl phthalate, fluorenes diether, methyl benzoate and dibutyl phthalate;

The quality percentage composition of described clay catalyst carrier in described clay load transition metal catalyst is 70.0～99.0%, is specially 75-90%;

The summation of the transition metal in the metallic element in described metallic compound and described transistion metal compound shared quality percentage composition in described clay load transition metal catalyst is 1.0～30.0%, is specially 1.0-10.0%;

When described metallic compound is magnesium-containing compound, the quality percentage composition of the transition metal in described transistion metal compound in described clay load transition metal catalyst is 0.5～5.0%;

When described metallic compound is aluminum contained compound, the quality percentage composition of the transition metal in described transistion metal compound in described clay load transition metal catalyst is 0.05～2.0%;

When described metallic compound is magnesium-containing compound and aluminum contained compound, the quality percentage composition of the transition metal in described transistion metal compound in described clay load transition metal catalyst is 0.55-7.0%.

The quality percentage composition of described internal electron donor in described clay load transition metal catalyst is 2.50-15.0%.

In addition; in the polypropylene that the clay that the invention described above provides strengthens, alloy, preparing vapour vehicle component, wrapping material, barrier material, fire retardant material, appliance material, material of construction and the daily life application at least one in material, also belongs to protection scope of the present invention.

The present invention utilizes catalyst-polymer particle shape print effect, is that on spherical clay load transition metal catalyst, situ catalytic propylene monomer and other monomers carry out polyreaction and make alloy resin in the polypropylene that clay strengthens at particle mode of appearance.The present invention has the following advantages:

1, the present invention focuses on the particle form of alloy in the polypropylene of clay enhancing is controlled, and a kind of method that can prepare alloy in the polypropylene with spheroidal particle mode of appearance is provided.Due to the spherical morphology of polypropylene product, thereby there is larger bulk density, in polymerization process, can not cause polymkeric substance to adhere to the phenomenon on still wall, thereby be easy to flow and transmission; Otherwise if polypropylene product is metamict, its bulk density is less, is easy to adhere on still wall, thereby affects the transmission of polymkeric substance, thereby limited its follow-up application prospect.

2, in the polypropylene that clay provided by the invention strengthens, in alloy, clay is dispersed in resin matrix with the form of limellar stripping, and known the present invention has successfully prepared alloy resin in the polypropylene that clay strengthens by in-situ polymerization.

3, in the interior alloy of polypropylene that clay provided by the invention strengthens, homopolymerization polyalphaolefin or the olefin copolymer introduced by second segment polymerization, for the performance diversity of alloy in polypropylene and high performance provide a new approach, further enrich the kind of acrylic resin, thereby provide broader application space for polypropylene.

In the polypropylene that this clay strengthens, alloy resin, in vapour vehicle component, wrapping material, barrier material, fire retardant material, appliance material, material of construction and daily life with fields such as materials, is all with a wide range of applications.

Accompanying drawing explanation

Fig. 1 is the apparent pattern of the interior alloy resin particle of polypropylene of argillaceous lamella in embodiment 1.

Fig. 2 is the wide-angle x-ray diffractogram of the interior alloy resin of polypropylene of argillaceous lamella in embodiment 1.

Fig. 3 is the transmission electron microscope photo of the interior alloy resin of polypropylene of argillaceous lamella in embodiment 1.

Fig. 4 is step 1 in embodiment 1) the intensification nuclear-magnetism carbon spectrogram of gained homo-polypropylene.

Fig. 5 is step 2 in embodiment 1) the intensification nuclear-magnetism carbon spectrogram of gained olefin polymer (ethylene, propylene random copolymers).

The apparent pattern of the transition-metal catalyst of Fig. 6 embodiment 1 medium clay soil load.

Fig. 7 is the wide-angle x-ray diffractogram of embodiment 1 medium clay soil carrier and clay load transition metal catalyst.

Fig. 8 is the mode of appearance containing alloy resin particle in the polypropylene of nano silicate lamella in embodiment 2.

Fig. 9 is the transmission electron microscope photo containing sample after alloy resin processing in the polypropylene of nano silicate lamella in embodiment 2.

Figure 10 is the apparent pattern of embodiment 2 medium clay soil loading transition metallic catalysts.

Embodiment

The clay Reinforced Polypropylene that following specific embodiment is just invented and the preparation method of copolymer resin make detailed explanation.But these embodiment are this restriction scope of invention not, also should not be construed as and only have condition provided by the invention, parameter or numerical value could implement the present invention.In clay load transition metal catalyst, the content of titanium elements and zr element all records by ultraviolet spectrophotometry, and in catalyzer, the content of magnesium elements and aluminium element all records by volumetry.The present invention focuses on the control of alloy polymers particle form in the polypropylene that clay is strengthened, thus to the sign of product mainly by two means: sem test (observing its form) and wide-angle x-ray diffraction are tested (deployment conditions of peeling off of testing clay layer).In following embodiment, each reaction is all carried out in inert atmosphere.

Embodiment 1

1) under vacuum state, 8g propylene monomer is filled with in the load of reactor soil, add successively 50ml solvent hexane, containing the n-heptane solution 3.5ml of 5.5mmol promotor triethyl aluminum and 0.1 gram of clay loaded transition-metal catalyst (in promotor triethyl aluminum, in aluminium element and clay loaded transition-metal catalyst, the mol ratio between transition metal titanium is 200: 1), in still, invariablenes pressure of liquid is at 0.7MPa, temperature of reaction is 70 ℃, carry out slurry polymerization 0.5 hour, obtain containing the mixture 6.0g of the homopolymerization isotatic polypropylene that clay and weight-average molecular weight are 365000g/mol, then, stop passing into propylene monomer,

2) to step 1) pass into gas mixture (wherein the mol ratio of ethene and propylene is 1: the 2) 2g of ethene and propylene in reactor, continue reaction 0.2 hour, in still, invariablenes pressure of liquid is 0.5MPa, temperature of reaction is 70 ℃, after having reacted, add acidifying ethanol to stop polyreaction, use deionized water and washing with alcohol, vacuum-drying at 60 ℃, obtains the interior alloy of polypropylene that 6.7 grams of clays strengthen;

Clay, homopolymerization isotatic polypropylene resin and ethylene/propylene olefinic random copolymer that in the polypropylene that this clay strengthens, alloy is 1.34: 88.46: 10.2 by mass ratio form.Particle mode of appearance is spherical, and as shown in Figure 1, grain diameter is 50～200 μ m; Wide-angle x-ray (as shown in Figure 2) and transmission electron microscope photo (as shown in Figure 3) all show, clay exists with the form of the nanoscale twins peeled off.By step 1) molecular structure of isotatic polypropylene is determined by the nuclear-magnetism carbon spectrum that heats up in gained mixture, as shown in Figure 4.By step 2) (molecular structure of ethylene/propylene olefinic random copolymer is definite by the nuclear-magnetism carbon spectrum that heats up, as shown in Figure 5 for gained olefin polymer.

Wherein, clay loaded transition-metal catalyst used is prepared as follows and obtains:

1) by 2.0g Magnesium Chloride Anhydrous MgCl ₂be scattered in 50ml decane with 5.5ml isooctyl alcohol, be heated to 130 ℃, form clear solution, at 130 ℃, react 2.0 hours, obtain magnesium chloride alcohol adduct;

Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension of clay catalyst carrier that 3.0g is spherical and 50ml decane, isothermal reaction 4.0 hours at 60 ℃, then filtering liquid, decane washing 3 times for the solid leaching, obtains the magnesium mixture of clay catalyst carrier after dry;

2) in the 100ml titanium tetrachloride solution of-20 ℃, add 5.0g step 1) the magnesium mixture of gained clay catalyst carrier, and isothermal reaction 1.0 hours at-20 ℃.Slowly be warming up to 120 ℃, add 0.2ml diisobutyl phthalate, isothermal reaction 1.5 hours at 120 ℃ afterwards, has reacted rear filtering liquid, again adds 100ml titanium tetrachloride solution, isothermal reaction 2.0 hours at 120 ℃.Finally, with hexane washing 3～6 times, after being dried, obtain clay loaded transition-metal catalyst.

This clay load transition metal catalyst is spheroidal particle (Fig. 6), by clay catalyst carrier, transistion metal compound Ti compound (TiCl ₄), internal electron donor diisobutyl phthalate and metallic compound magnesium compound (magnesium chloride) composition; Wherein, the content of titanium elements, magnesium elements is respectively 1.34wt%, 2.15wt%, and the content of diisobutyl phthalate and clay catalyst carrier is respectively 5.9wt%, 75wt%.

This clay catalyst carrier medium clay soil sheet interlayer spacing is 2.0nm, and on the wide-angle x-ray diffractogram (Fig. 7) of clay load transition metal catalyst, (001) face characteristic peak of clay layer moves to low angle, and this characteristic peak broadens, clay load transition metal catalyst medium clay soil sheet interlayer spacing is greater than 2.0nm, this explanation catalytic active component entered between clay layer and be uniformly distributed in clay load transition metal catalyst particle inside and outside.Nitrogen adsorption test result is known, and the specific surface area of this clay load transition metal catalyst is 137.5m ²/ g, pore volume is 0.36cm ³/ g, mean pore size is 16.7nm.

Wherein, step 1) clay catalyst carrier used, prepare by the following method:

1) 10 grams of sodium-based montmorillonites are scattered in the mixing solutions of 500 ml waters and 500 milliliters of ethanol and form suspension, in this suspension, add 12 grams of palmityl trimethyl ammonium chlorides, at 80 ℃, react after 4.0 hours and filter, use respectively 200 ml waters and washing with alcohol three times, vacuum-drying 20.0 hours at 80 ℃ again, obtains the organic clay through octadecyl trimethyl ammonium chloride modification.

2) at 60 ℃, in 100ml reaction flask, add successively 0.3578 gram of strong aqua, 1.3694 grams of deionized waters and 22.7572 grams of dehydrated alcohols, magnetic agitation, after 0.5 hour, is added dropwise to 1.0000 grams of tetraethoxys.At 60 ℃, react 4.0 hours.Then except desolventizing, after being dried, obtain reactive silicon dioxide nanoparticle, its median size is 40nm.

3) get 20 grams of dry steps 1) gained is through the organic clay of octadecyl trimethyl ammonium chloride modification, is scattered in (mass percentage concentration of organic clay in this suspension is 6.2wt%) in 400 milliliters of ethanol through ultrasonication.At 60 ℃, by 93.98 grams of steps 2) (wherein, the mass percentage concentration of reactive silicon dioxide nanoparticle is 1.12wt% for the alcohol suspension of gained reactive silicon dioxide nanoparticle; The mass ratio of reactive silicon dioxide nanoparticle and organic clay is 1: 19) be added dropwise in homodisperse organic clay suspension.After being added dropwise to complete, react 4.0 hours, then add 2.0 grams of bicarbonate of ammonia (mass ratio of bicarbonate of ammonia and organic clay is 0.1: 1), continue to stir after 0.5 hour, spray drying forming obtains clay catalyst carrier.

(the organic intercalation agent octadecyl dimethyl hydroxyethyl ammonium nitrate and the sodium-based montmorillonite that are 20: 80 by mass ratio form the clay through organic intercalation agent modification that this clay catalyst carrier is 95: 5 by mass ratio, the character of sodium-based montmorillonite is as follows: cation exchange capacity is 90meq/100g, and specific surface area is 17.89m ²/ g, mean pore size is 21.90nm, pore volume is 0.10cm ³/ g, sheet interlayer spacing is 1.0nm) and the median size reactive silicon dioxide composition that is 40nm, its particle form is spherical, and its grain diameter is 10～30 μ m, and specific surface area is 42.1m ²/ g, pore volume is 0.18cm ³/ g, mean pore size is 13.4nm.The wide-angle x-ray diffraction test result of clay catalyst carrier and organic clay is known, within the scope of 1.5 °～10 °, all there is (001) face characteristic peak of clay in diffraction angle, calculate according to Bragg equation 2dsin θ=λ, its sheet interlayer spacing is 2.0nm, and this explanation sheet interlayer spacing is not because changing adding of reactive silicon dioxide nanoparticle.

Embodiment 2

1) 250 grams of propylene liquids are added in reactor, at 30 ℃, add successively containing 0.25mol promotor triethyl aluminum, (in the aluminium element in triethyl aluminum and clay load transition metal catalyst, the mol ratio of transition metal titanium is 600: 1 for 0.05mol promotor methylaluminoxane and 1.0 grams of clay load transition metal catalysts; In aluminium element in methylaluminoxane and catalyzer, the mol ratio of transition metal zirconium is 2000: 1) and hydrogen 0.2g, pressure is 3.1MPa, be warming up to 70 ℃, carry out bulk polymerization 0.2 hour, obtain the mixture that 104.28g contains the homopolymerization isotatic polypropylene that clay and weight-average molecular weight are 660000g/mol, directly carry out next step reaction.

2) by above-mentioned steps 1) in reactor in residual propylene emptying be cooled to 50 ℃, pass into again the gas mixture of 20g ethene and 60g propylene, pass into hydrogen 0.05g, pressure is 1.0MPa, be warming up to 90 ℃, carry out polyreaction 0.2 hour, finally obtain the interior alloy 120.0g of polypropylene that clay strengthens.

Clay, homopolymerization isotatic polypropylene resin and ethylene/propylene olefinic random copolymer that in the polypropylene that this clay strengthens, alloy is 0.82: 86.08: 13.1 by mass ratio form.The polypropylene alloy particle mode of appearance that this clay strengthens is spherical, and as shown in Figure 8, grain diameter is 50～200 μ m; Wide-angle x-ray test result shows that transmission electron microscope photo (Fig. 9) all shows, nanoclay exists with the form of the nanoscale twins peeled off.

Wherein, clay load transition metal catalyst used is prepared by the following method:

1) by 2.0g Magnesium Chloride Anhydrous MgCl ₂be scattered in 20ml decane with 5.5ml isooctyl alcohol, be heated to 110 ℃, form clear solution, at 110 ℃, react 4.0 hours.

Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension of the spherical clay carrier/100ml of 3.0g decane, isothermal reaction 12.0 hours at 90 ℃, then filtering liquid, decane washing 3 times for the solid leaching, obtains the magnesium mixture of clay catalyst carrier after dry.

2) to the magnesium mixture that adds the spherical described clay catalyst carrier of 10.0g in the 100ml titanium tetrachloride solution of-20 ℃, and isothermal reaction 1.0 hours at-20 ℃.Slowly be warming up to 110 ℃, add 0.3ml diisobutyl phthalate, then isothermal reaction 2.0 hours at 110 ℃, has reacted rear filtering liquid, again adds 100ml titanium tetrachloride solution, isothermal reaction 2.0 hours at 120 ℃.Finally, with hexane washing 3～6 times, after being dried, obtain clay loaded titanium compound.

3) getting 5.0 grams of described spherical clay loaded titanium compounds is scattered in 50ml toluene, then add the toluene solution 30ml containing 0.05mol methylaluminoxane, at 90 ℃, react 10.0 hours, then use toluene wash 5 times, after being dried, obtain the clay catalyst of activation.

4) by 0.15 gram of transistion metal compound rac-Me ₂si (2-Me-4-PhInd) ₂zrCl ₂be added in the toluene solution 40ml that contains 0.10mol methylaluminoxane, at 0 ℃, react 4.0 hours, obtain the catalyst solution of activation.

5) this catalyst solution is added dropwise to containing 5.0 grams of described steps 3) prepare in the 50ml toluene suspension of clay catalyst of gained activation, at 90 ℃, react 4.0 hours.After having reacted, use toluene wash 5 times, after being dried, obtain clay loaded transition-metal catalyst provided by the invention.

This clay load transition metal catalyst is spheroidal particle, as shown in figure 10.By clay catalyst carrier, transistion metal compound titanium compound (TiCl ₄), internal electron donor diisobutyl phthalate and zirconium compounds (rac-Me ₂si (2-Me-4-PhInd) ₂zrCl ₂) and magnesium compound (MgCl ₂) and aluminum compound (methylaluminoxane) composition, wherein the content of titanium elements, magnesium elements, zr element and aluminium element is respectively 1.98wt%, 3.01wt%, 0.20wt%, 7.98wt%, and the content of diisobutyl phthalate is 10.02wt%.The quality percentage composition of clay catalyst carrier is 72%.Wide-angle x-ray diffraction test result, wherein clay layer spacing is greater than 2.0nm, and catalytic active component enters clay layer gap and is uniformly distributed in inside and outside clay load transition metal catalyst particle.The specific surface area of this catalyzer is 56.8m ²/ g, pore volume is 0.16cm ³/ g, mean pore size is 14.4nm.

Wherein, clay catalyst carrier used, prepare by the following method:

1) through the preparation of the organic clay of octadecyl trimethyl ammonium chloride modification: 10 grams of sodium-based montmorillonites are scattered in the mixing solutions of 500 ml waters and 500 milliliters of ethanol and form suspension, in this suspension, add 12 grams of palmityl trimethyl ammonium chlorides, at 80 ℃, react after 4.0 hours and filter, use respectively 200 ml waters and washing with alcohol three times, vacuum-drying 20.0 hours at 80 ℃ again, obtains the organic clay through octadecyl trimethyl ammonium chloride modification.

2) preparation of reactive silicon dioxide nanoparticle: at 60 ℃, in 100ml reaction flask, add successively 0.3578 gram of strong aqua, 1.3694 grams of deionized waters and 22.7572 grams of dehydrated alcohols, magnetic agitation, after 0.5 hour, is added dropwise to 1.0000 grams of tetraethoxys.At 60 ℃, react 4.0 hours.Then except desolventizing, after being dried, obtain reactive silicon dioxide nanoparticle, its median size is 40nm.

3) preparation of clay catalyst carrier: get 20 grams of dry described organic claies through octadecyl trimethyl ammonium chloride modification, be scattered in (mass percentage concentration of organic clay in this suspension is 6.2wt%) in 400 milliliters of ethanol through ultrasonication.At 60 ℃, by the alcohol suspension of 93.98 grams of reactive silicon dioxide nanoparticles, (wherein, the mass percentage concentration of reactive silicon dioxide nanoparticle is 1.12wt%; The mass ratio of reactive silicon dioxide nanoparticle and organic clay is 1: 19) be added dropwise in homodisperse organic clay suspension.After being added dropwise to complete, react 4.0 hours, then add 2.0 grams of bicarbonate of ammonia (mass ratio of bicarbonate of ammonia and organic clay is 0.1: 1), continue to stir after 0.5 hour, spray drying forming prepares clay catalyst carrier.

(organic intercalation agent octadecyl dimethyl hydroxyethyl ammonium nitrate and sodium-based montmorillonite that organic clay is 20: 80 by mass ratio form the organic clay that this clay catalyst carrier is 95: 5 by mass ratio, the character of sodium-based montmorillonite is as follows: cation exchange capacity is 90meq/100g, and specific surface area is 17.89m ²/ g, mean pore size is 21.90nm, pore volume is 0.10cm ³/ g, sheet interlayer spacing is 1.0nm) and the median size reactive silicon dioxide composition that is 40nm, its particle form is spherical, and its grain diameter size is 10～30 μ m, and specific surface area is 42.1m ²/ g, pore volume is 0.18cm ³/ g, mean pore size is 13.4nm.The wide-angle x-ray diffraction test result of clay catalyst carrier and organic clay is known, within the scope of 1.5 °～10 °, all there is (001) face characteristic peak of clay in diffraction angle, calculate according to Bragg equation 2dsin θ=λ, its sheet interlayer spacing is 2.0nm, and this explanation sheet interlayer spacing is not because changing adding of reactive silicon dioxide nanoparticle.

Embodiment 3

1) 250 grams of propylene liquids are added in reactor, at 30 ℃, add successively 0.15mol promotor triethyl aluminum and 1.0 grams of clay load transition metal catalysts (in triethyl aluminum, in aluminium element and clay load transition metal catalyst, the mol ratio of titanium elements is 400: 1), be warming up to 70 ℃, pressure is 3.1MPa, carry out bulk polymerization 0.5 hour, the mixture 133g that obtains containing the homopolymerization isotatic polypropylene that clay and weight-average molecular weight are 785000g/mol, directly carries out next step reaction.

2) by above-mentioned steps 1) in reactor in residual propylene emptying be cooled to 50 ℃, then pass into 50 grams of ethylene gas, pass into hydrogen 0.05g, be warming up to 90 ℃, pressure is 1.0MPa, carries out polyreaction 1 hour, finally obtains alloy 180.0g in clay Reinforced Polypropylene still.

Clay, homopolymerization isotatic polypropylene resin and homopolymerisation polyethylene that in the polypropylene that this clay strengthens, alloy is 0.56: 74.24: 25.2 by mass ratio form.This clay Reinforced Polypropylene alloying pellet mode of appearance is spherical, and particle diameter is 50～500 μ m; Wide-angle x-ray test result shows, clay exists with the nanoscale twins form of peeling off.

2) in the 100ml titanium tetrachloride solution of-20 ℃, add 10.0g step 1) the magnesium mixture of the spherical clay catalyst carrier of gained, and isothermal reaction 1.0 hours at-20 ℃.Slowly be warming up to 80 ℃, add the then isothermal reaction 2.0 hours at 110 ℃ of 2.0 grams of fluorenes diether, reacted rear filtering liquid, again add 100ml titanium tetrachloride solution, isothermal reaction 2.0 hours at 120 ℃.Finally, with hexane washing 3～6 times, after being dried, obtain clay loaded transition-metal catalyst.

This clay load transition metal catalyst is spheroidal particle, by clay catalyst carrier, transistion metal compound titanium compound (TiCl ₄) form with magnesium chloride and internal electron donor fluorenes diether, wherein the content of titanium elements, magnesium elements is respectively 1.89wt% and 3.53wt%, and the content of fluorenes diether is 13.72wt%.Wide-angle x-ray diffraction test result, wherein clay layer spacing is greater than 2.0nm, and catalytic active component enters clay layer gap and is uniformly distributed in inside and outside clay load transition metal catalyst particle.The specific surface area of this clay load transition metal catalyst is 47.9m ²/ g, pore volume is 0.15cm ³/ g, mean pore size is 12.7nm.

Wherein, clay catalyst carrier used, prepare by the following method:

3) preparation of clay catalyst carrier: get 20 grams of dry described organic claies through octadecyl trimethyl ammonium chloride modification, be scattered in (mass percentage concentration of organic clay in this suspension is 6.2wt%) in 400 milliliters of ethanol through ultrasonication.At 60 ℃, by the alcohol suspension of 93.98 grams of reactive silicon dioxide nanoparticles, (wherein, the mass percentage concentration of reactive silicon dioxide nanoparticle is 1.12wt%; The mass ratio of reactive silicon dioxide nanoparticle and organic clay is 1: 19) be added dropwise in homodisperse organic clay suspension.After being added dropwise to complete, react 4.0 hours, then add 2.0 grams of bicarbonate of ammonia (mass ratio of bicarbonate of ammonia and organic clay is 0.1: 1), continue to stir after 0.5 hour, spray drying forming obtains clay catalyst carrier.

(organic intercalation agent octadecyl dimethyl hydroxyethyl ammonium nitrate and sodium-based montmorillonite that organic clay is 15: 85 by mass ratio form the organic clay that this clay catalyst carrier is 90: 10 by mass ratio, the character of sodium-based montmorillonite is as follows: cation exchange capacity is 90meq/100g, and specific surface area is 17.89m ²/ g, mean pore size is 21.90nm, pore volume is 0.10cm ³/ g, sheet interlayer spacing is 1.0nm) and the median size reactive silicon dioxide composition that is 40nm, its particle form is spherical, and its grain diameter is 10～30 μ m, and specific surface area is 44.78m ²/ g, pore volume is 0.22cm ³/ g, mean pore size is 11.6nm.The wide-angle x-ray diffraction test result of clay catalyst carrier and organic clay is known, within the scope of 1.5 °～10 °, all there is (001) face characteristic peak of clay in diffraction angle, calculate according to Bragg equation 2dsin θ=λ, its sheet interlayer spacing is 2.0nm, and this explanation sheet interlayer spacing is not because changing adding of reactive silicon dioxide nanoparticle.

Embodiment 4

1) 250 grams of propylene liquids are added in reactor, (in triethyl aluminum, in aluminium element and clay load transition metal catalyst, the mol ratio of titanium elements is 700: 1 to add successively 0.2mol promotor triethyl aluminum, 0.02mol external electron donor dimethyl diphenyl silane and 1.0 grams of clay load transition metal catalysts at 30 ℃; In external electron donor dimethyl diphenyl silane and clay load transition metal catalyst, the mol ratio of titanium elements is 0.1: 1) and hydrogen 0.2g, be warming up to 70 ℃, pressure is 3.1MPa, carry out bulk polymerization 0.2 hour, the mixture 104g that obtains containing the homopolymerization isotatic polypropylene that clay and weight-average molecular weight are 300000g/mol, directly carries out next step reaction.

2) by above-mentioned steps 1) in reactor in residual propylene emptying be cooled to 50 ℃, then pass into 20g1-butylene, pass into hydrogen 0.03g, be warming up to 50 ℃, pressure is 2.5MPa, carries out polyreaction 0.5 hour, finally obtains alloy 110.0g in clay Reinforced Polypropylene still.

Clay, homopolymerization isotatic polypropylene resin and homopolymerization isotactic poly-1-butylene that in the polypropylene that this clay strengthens, alloy is 0.64: 93.81: 5.55 by mass ratio form.Particle mode of appearance is spherical, and grain diameter is 50～500 μ m; Wide-angle x-ray test result shows, clay exists with the form of the nanoscale twins peeled off.

2) to the magnesium mixture that adds the spherical described clay catalyst carrier of 10.0g in the 100ml titanium tetrachloride solution of-20 ℃, and isothermal reaction 1.0 hours at-20 ℃.Slowly be warming up to 80 ℃, add 0.3ml diisobutyl phthalate, then isothermal reaction 2.0 hours at 110 ℃, has reacted rear filtering liquid, again adds 100ml titanium tetrachloride solution, isothermal reaction 2.0 hours at 120 ℃.Finally, with hexane washing 3～6 times, after being dried, obtain clay loaded titanium compound.

3) getting 5.0 grams of described spherical clay loaded titanium compounds is scattered in 100ml toluene, then add the toluene solution 30ml containing 0.1mol methylaluminoxane, at 110 ℃, react 4.0 hours, then use toluene wash 5 times, after being dried, obtain the clay catalyst of activation.

4) by 0.20 gram of transistion metal compound Et (Ind) ₂zrCl ₂be added in the toluene solution 80ml that contains 0.20mol methylaluminoxane, at 20 ℃, react 4.0 hours, obtain the catalyst solution of activation.

This clay load transition metal catalyst is spheroidal particle, by clay catalyst carrier, transistion metal compound titanium compound (TiCl ₄) and zirconium compounds (Et (Ind) ₂zrCl ₂) metallizing thing magnesium compound (magnesium chloride) and aluminum compound (methylaluminoxane) and internal electron donor diisobutyl phthalate composition, wherein the content of titanium elements, magnesium elements, zr element, aluminium element is respectively 1.34wt%, 2.89wt%, 0.30wt% and 14.68wt%, and the content of diisobutyl phthalate and clay catalyst carrier is for being respectively 9.78wt% and 70wt%.Wide-angle x-ray diffraction test result, wherein clay layer spacing is greater than 2.0nm, and catalytic active component enters clay layer gap and is uniformly distributed in inside and outside clay load transition metal catalyst particle.The specific surface area of this catalyzer is 47.9m ²/ g, pore volume is 0.15cm ³/ g, mean pore size is 12.7nm.

Wherein, clay catalyst carrier used, prepare by the following method:

(organic intercalation agent octadecyl dimethyl hydroxyethyl ammonium nitrate and sodium-based montmorillonite that organic clay is 20: 80 by mass ratio form the organic clay that this clay catalyst carrier is 95: 5 by mass ratio, the character of sodium-based montmorillonite is as follows: cation exchange capacity is 90meq/100g, and specific surface area is 17.89m ²/ g, mean pore size is 21.90nm, pore volume is 0.10cm ³/ g, sheet interlayer spacing is 1.0nm) and the median size reactive silicon dioxide composition that is 40nm, its particle form is spherical, and its grain diameter is 10～30 μ m, and specific surface area is 42.1m ²/ g, pore volume is 0.18cm ³/ g, mean pore size is 13.4nm.The wide-angle x-ray diffraction test result of clay catalyst carrier and organic clay is known, within the scope of 1.5 °～10 °, all there is (001) face characteristic peak of clay in diffraction angle, calculate according to Bragg equation 2dsin θ=λ, its sheet interlayer spacing is 2.0nm, and this explanation sheet interlayer spacing is not because changing adding of reactive silicon dioxide nanoparticle.

Embodiment 5

1) 250 grams of propylene liquids are added in reactor, at 30 ℃, add successively 0.25mol promotor triisobutyl aluminium and 1.0 grams of clay load transition metal catalysts (in triisobutyl aluminium, in aluminium element and clay load transition metal catalyst, the mol ratio of titanium elements is 460: 1) and hydrogen 0.2g, be warming up to 70 ℃, pressure is 3.2MPa, carry out bulk polymerization 0.2 hour, the mixture 108g that obtains containing the homopolymerization isotatic polypropylene that clay and weight-average molecular weight are 400000g/mol, directly carries out next step reaction.

2) by above-mentioned steps 1) in reactor in residual propylene emptying be cooled to 50 ℃, pass into again the gas mixture of 20g propylene and 40g1-butylene, pass into hydrogen 0.03g, be warming up to 90 ℃, pressure is 1.2MPa, carry out polyreaction 0.2 hour, finally obtain alloy 125.0g in clay Reinforced Polypropylene still.

Clay, homopolymerization isotatic polypropylene resin and propylene/1-butene random copolymer that in the polypropylene that this clay strengthens, alloy is 0.67: 86.83: 5.55 by mass ratio form.Particle mode of appearance is spherical, and grain diameter is 50～500 μ m; Wide-angle x-ray test result shows, clay exists with the form of the nanoscale twins peeled off.

Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension of the spherical clay carrier of 3.0g and 50ml decane, isothermal reaction 4.0 hours at 60 ℃, then filtering liquid, decane washing 3 times for the solid leaching, obtains the magnesium mixture of clay catalyst carrier after dry;

2) to the magnesium mixture that adds clay catalyst carrier described in 5.0g in the 100ml titanium tetrachloride solution of-20 ℃, and isothermal reaction 1.0 hours at-20 ℃.Slowly be warming up to 120 ℃, add 0.5 gram of fluorenes diether, isothermal reaction 1.5 hours at 120 ℃ afterwards, has reacted rear filtering liquid, again adds 100ml titanium tetrachloride solution, isothermal reaction 2.0 hours at 120 ℃.Finally, with hexane washing 3～6 times, after being dried, obtain clay loaded transition-metal catalyst provided by the invention.

This clay load transition metal catalyst is in spheroidal particle, by clay catalyst carrier, transistion metal compound TiCl ₄, MgCl ₂form with internal electron donor fluorenes diether; Wherein the content of titanium elements, magnesium elements is respectively 2.56wt%, 2.15wt%, and the content of fluorenes diether and clay catalyst carrier is respectively 10.5wt% and 65wt%.In wide-angle x-ray diffraction test result, clay layer spacing is greater than 2.0nm, and catalytic active component enters clay layer gap and is uniformly distributed in inside and outside clay load transition metal catalyst particle.The specific surface area of this catalyzer is 42.1m ²/ g, pore volume is 0.18cm ³/ g, mean pore size is 13.4nm.

Wherein, clay catalyst carrier used, prepare by the following method:

(organic intercalation agent octadecyl dimethyl hydroxyethyl ammonium nitrate and sodium-based montmorillonite that organic clay is 20: 80 by mass ratio form the organic clay that this clay catalyst carrier is 95: 5 by mass ratio, the character of sodium-based montmorillonite is as follows: cation exchange capacity is 90meq/100g, and specific surface area is 17.89m ²/ g, mean pore size is 21.90nm, pore volume is 0.10cm ³/ g, sheet interlayer spacing is 1.0nm) and the median size reactive silicon dioxide composition that is 40nm, its particle form is spherical, and its grain diameter is 10～30 μ m, and specific surface area is 42.1m ²/ g, pore volume is 0.18cm ³/ g, mean pore size is 13.4nm.Wide-angle x-ray diffraction test result is known, on the diffractogram of clay catalyst carrier prepared by this method and organic clay, show, within the scope of 1.5 °～10 °, all there is (001) face characteristic peak of clay in diffraction angle, calculate according to Bragg equation 2dsin θ=λ, its sheet interlayer spacing is 2.0nm, and this explanation sheet interlayer spacing is not because changing adding of reactive silicon dioxide nanoparticle.

Embodiment 6

1) 250 grams of propylene liquids are added in reactor, at 30 ℃, add successively 0.25mol promotor triethyl aluminum and 1.0 grams of clay load transition metal catalysts (in triethyl aluminum, in aluminium element and clay load transition metal catalyst, between titanium elements, mol ratio is 460: 1) and hydrogen 0.1g, be warming up to 75 ℃, pressure is 3.1MPa, carry out bulk polymerization 0.2 hour, the mixture 134.8g that obtains containing the homopolymerization isotatic polypropylene that clay and weight-average molecular weight are 560000g/mol, directly carries out next step reaction.

2) by above-mentioned steps 1) in reactor in residual propylene emptying be cooled to 50 ℃, pass into again the gas mixture of 5g propylene and 80g1-butylene, pass into hydrogen 0.03g, be warming up to 90 ℃, pressure is 1.0MPa, carry out polyreaction 1.0 hours, finally obtain the interior alloy 175.0g of polypropylene that clay strengthens.

Clay, homopolymerization isotatic polypropylene resin and propylene/1-butene random copolymer that in the polypropylene that this clay strengthens, alloy is 0.45: 77.05: 22.5 by mass ratio form.Particle mode of appearance is spherical, and grain diameter size is 50～500 μ m; Wide-angle x-ray test result shows, clay exists with the form of the nanoscale twins peeled off.

This clay load transition metal catalyst is spheroidal particle, by clay catalyst carrier, transistion metal compound TiCl ₄, MgCl ₂form with internal electron donor fluorenes diether; Wherein the content of titanium elements, magnesium elements is respectively 2.56wt% and 2.15wt%, and the content of fluorenes diether and clay catalyst carrier is respectively 10.5wt% and 65wt%.Wide-angle x-ray diffraction test result, identical with Fig. 7, no longer repeat, wherein clay layer spacing is greater than 2.0nm, and catalytic active component enters clay layer gap and is uniformly distributed in inside and outside clay load transition metal catalyst particle.The specific surface area of this catalyzer is 42.1m ²/ g, pore volume is 0.18cm ³/ g, mean pore size is 13.4nm.

Wherein, clay catalyst carrier used, prepare by the following method:

3) preparation of clay catalyst carrier: get 20 grams of dry described organic claies through octadecyl trimethyl ammonium chloride modification, be scattered in (concentration of organic clay in this suspension is 6.2wt%) in 400 milliliters of ethanol through ultrasonication.At 60 ℃, by the alcohol suspension of 93.98 grams of reactive silicon dioxide nanoparticles, (wherein, the mass percentage concentration of reactive silicon dioxide nanoparticle is 1.12wt%; The mass ratio of reactive silicon dioxide nanoparticle and organic clay is 1: 19) be added dropwise in homodisperse organic clay suspension.After being added dropwise to complete, react 4.0 hours, then add 2.0 grams of bicarbonate of ammonia (mass ratio of bicarbonate of ammonia and organic clay is 0.1: 1), continue to stir after 0.5 hour, spray drying forming prepares clay catalyst carrier.

Embodiment 7

1) 250 grams of propylene liquids are added in reactor, at 30 ℃, add successively 0.25mol promotor triethyl aluminum and 1.0 grams of clay load transition metal catalysts (in triethyl aluminum, in aluminium element and clay load transition metal catalyst, the mol ratio between titanium elements is 460: 1) and hydrogen 0.05g, be warming up to 75 ℃, pressure is 3.0MPa, carry out bulk polymerization 0.2 hour, the mixture 107g that obtains containing the homopolymerization isotatic polypropylene that clay and weight-average molecular weight are 620000g/mol, directly carries out next step reaction.

2) by above-mentioned steps 1) in reactor in residual propylene emptying be cooled to 50 ℃, pass into again 40g ethene and 5g1-octene, pass into hydrogen 0.03g, be warming up to 90 ℃, pressure is 1.7MPa, carry out polyreaction 1.0 hours, finally obtain alloy 115.0g in clay Reinforced Polypropylene still.

Clay, homopolymerization isotatic polypropylene resin and ethene/1-octene random copolymers that in the polypropylene that this clay strengthens, alloy is 1.42: 92.98: 5.6 by mass ratio form.Particle mode of appearance is spherical, and grain diameter size is 50～500 μ m; Wide-angle x-ray test result shows, clay exists with the form of the nanoscale twins peeled off.

2) to the magnesium mixture that adds clay catalyst carrier described in 5.0g in the 100ml titanium tetrachloride solution of-20 ℃, and isothermal reaction 1.0 hours at-20 ℃.Slowly be warming up to 120 ℃, add 0.2ml diisobutyl phthalate, isothermal reaction 1.5 hours at 120 ℃ afterwards, has reacted rear filtering liquid, again adds 100ml titanium tetrachloride solution, isothermal reaction 2.0 hours at 120 ℃.Finally, with hexane washing 3～6 times, after being dried, obtain clay loaded transition-metal catalyst provided by the invention.

This clay load transition metal catalyst is spheroidal particle, by clay catalyst carrier, transistion metal compound TiCl ₄, MgCl ₂form with internal electron donor fluorenes diether; Wherein the content of titanium elements, magnesium elements is respectively 2.56wt%, 2.15wt%, and the content of fluorenes diether and clay catalyst carrier is respectively 10.5wt%, 65wt%.The wide-angle x-ray diffraction test result of this catalyzer is identical with Fig. 7, no longer repeats, and wherein clay layer spacing is greater than 2.0nm, and catalytic active component enters clay layer gap and is uniformly distributed in inside and outside clay load transition metal catalyst particle.The specific surface area of this catalyzer is 42.1m ²/ g, pore volume is 0.18cm ³/ g, mean pore size is 13.4nm.

Wherein, clay catalyst carrier used, prepare by the following method:

Embodiment 8

1) 250 grams of propylene liquids are added in reactor, at 30 ℃, add successively 0.25mol promotor triethyl aluminum and 1.0 grams of clay load transition metal catalysts and hydrogen 0.2g, in triethyl aluminum, in aluminium element and clay load transition metal catalyst, the mol ratio between titanium elements is 460: 1, be warming up to 70 ℃, pressure is 3.1MPa, carry out bulk polymerization 0.5 hour, the mixture 97.14g that obtains containing the homopolymerization isotatic polypropylene that clay and weight-average molecular weight are 320000g/mol, directly carries out next step reaction.

2) by above-mentioned steps 1) in reactor in residual propylene emptying be cooled to 50 ℃, then pass into 30g1-octene, pass into hydrogen 0.03g, be warming up to 60 ℃, pressure is 1.0MPa, carries out polyreaction 2 hours, finally obtains the interior alloy 102.0g of polypropylene that clay strengthens.

The poly-1-octene of clay, homopolymerization isotatic polypropylene resin and homopolymerization isotactic that in the polypropylene that this clay strengthens, alloy is 2.0: 95.5: 2.5 by mass ratio forms.Particle mode of appearance is spherical, and grain diameter is 50～500 μ m; Wide-angle x-ray test result shows, clay exists with the form of the nanoscale twins peeled off.

This clay load transition metal catalyst is spheroidal particle, by clay catalyst carrier, transistion metal compound TiCl ₄, MgCl ₂form with internal electron donor fluorenes diether; Wherein the content of titanium elements, magnesium elements is respectively 2.56wt%, 2.15wt%, and the content of fluorenes diether and clay catalyst carrier is respectively 10.5wt%, 65wt%.Wide-angle x-ray diffraction test result, identical with Fig. 7, no longer repeat, wherein clay layer spacing is greater than 2.0nm, and catalytic active component enters clay layer gap and is uniformly distributed in inside and outside granules of catalyst.The specific surface area of this catalyzer is 42.1m ²/ g, pore volume is 0.18cm ³/ g, mean pore size is 13.4nm.

Wherein, clay catalyst carrier used, prepare by the following method:

Embodiment 9

Respectively according to standard ISO 527-2-5A (Elongation test), the mechanical property of alloy in the polypropylene that ASTM 638-V (crooked test) and ASTMD256-02 (impact property test) sample preparation test implementation example 1,2 and 5 gained clays strengthen, test result is as shown in table 1.

The mechanical experimental results of alloy in the polypropylene that table 1, clay strengthen

The preparation method of this comparative sample is as follows:

1) under vacuum state, 20g propylene monomer is filled with in reactor, add successively 50ml solvent hexane, containing n-heptane solution 3.5ml and 0.02 gram of magnesium chloride load transition-metal catalyst (in promotor triethyl aluminum, in the transition-metal catalyst of aluminium element and magnesium chloride load, the mol ratio between transition metal titanium is 150: 1) of 1.5mmol promotor triethyl aluminum, in still, invariablenes pressure of liquid is at 0.7MPa, temperature of reaction is 70 ℃, carry out slurry polymerization 0.5 hour, obtain the homo-polypropylene 15.0g that weight-average molecular weight is 420000g/mol, then, stop passing into propylene monomer,

2) to step 1) pass into gas mixture (wherein the mol ratio of ethene and propylene is 1: the 2) 5g of ethene and propylene in reactor, continue reaction 0.2 hour, in still, invariablenes pressure of liquid is 0.5MPa, temperature of reaction is 70 ℃, after having reacted, add acidifying ethanol to stop polyreaction, use deionized water and washing with alcohol, vacuum-drying at 60 ℃, obtains alloy in 17.0 grams of polypropylenes;

Homo-polypropylene resin and ethylene/propylene olefinic random copolymer that in this polypropylene, alloy is 88.24% and 11.76% by mass ratio form.

Wherein, the transition-metal catalyst of magnesium chloride load used is prepared as follows and obtains:

2) in the 100ml titanium tetrachloride solution of-20 ℃, being added dropwise to step 1) gained is above-mentioned magnesium chloride alcohol adduct, and isothermal reaction 1.0 hours at-20 ℃.Slowly be warming up to 120 ℃, add 0.2ml diisobutyl phthalate, isothermal reaction 1.5 hours at 120 ℃ afterwards, has reacted rear filtering liquid, again adds 100ml titanium tetrachloride solution, isothermal reaction 2.0 hours at 120 ℃.Finally, with hexane washing 3～6 times, after being dried, obtain the transition-metal catalyst of magnesium chloride load.

This magnesium chloride load transition-metal catalyst is made up of magnesium chloride, titanium tetrachloride and internal electron donor diisobutyl phthalate; The content of titanium elements, magnesium elements is respectively 2.32wt%, 17.56wt%, and the content of diisobutyl phthalate is 9.88wt%.

As from the foregoing, in the polypropylene that clay provided by the invention strengthens, alloy has higher modulus and impelling strength, thereby has realized the target of high-modulus and high tenacity simultaneously, has obtained the interior alloy of polypropylene of excellent performance.With alloy phase ratio in polypropylene not argillaceous, its every mechanical property is all improved to some extent.

In the polypropylene that all the other embodiment gained clays strengthen, the mechanical property detected result of alloy and upper without substantive difference repeats no more herein.

Claims

1. alloy in the polypropylene that clay strengthens, comprises clay, homo-polypropylene resin and olefin polymer.

2. alloy in polypropylene according to claim 1, is characterized in that: described homo-polypropylene resin is selected from least one in isotatic polypropylene, syndiotactic polypropylene and Atactic Polypropelene resin,

The weight-average molecular weight of described homo-polypropylene resin is 20000-1000000g/mol, is specially 200000-800000g/mol; Or,

Described olefin polymer is the polymkeric substance being obtained by one or both monomer polymerization reaction take places in alpha-olefin; Wherein, described alpha-olefin is ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-nonene or 1-decene; Or,

The mass ratio of described homo-polypropylene resin and described olefin polymer is 40.0～99.0: 1.0～60.0, is specially 60-95: 5-40;

The quality percentage composition that described clay accounts for the interior alloy of polypropylene of described clay enhancing is 0.01-25%, is specially 0.2-5%.

3. according to alloy in the arbitrary described polypropylene of claim 1 or 2, it is characterized in that: in the polypropylene that described clay strengthens, the particle mode of appearance of alloy is spherical, and particle diameter is 10～10000 μ m, is specially 50-1000 μ m; Or,

4. a method of preparing the interior alloy of polypropylene of the arbitrary described clay enhancing of claim 1-3, comprises the steps:

Or, propylene monomer and clay load transition metal catalyst, promotor are carried out to bulk polymerization, react the complete mixture that contains clay and homo-polypropylene of obtaining;

5. method according to claim 4, it is characterized in that: described promotor is selected from least one in the aluminum alkyls of C1-C4 and the aluminum alkoxide of C1-C4, is specifically selected from least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and methylaluminoxane; Or,

Described alhpa olefin is ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-nonene or 1-decene.

6. according to the method described in claim 4 or 5, it is characterized in that: described step 1) in, in the aluminium element in promotor and clay load transition metal catalyst, the mol ratio of transition metal is 1～5000: 1, is specially 10-2000: 1; Or,

The add-on of described clay load transition metal catalyst is the 0.1-20% of described propylene monomer quality, is specially 0.4-10%;

Described step 2) in, the add-on of described alpha-olefin is 0.5～80.0% of the described step 1 gained mixture quality that contains clay and homo-polypropylene resin, is specially 1-80%.

7. according to the arbitrary described method of claim 4-6, it is characterized in that: described step 1) in, the temperature of described slurry polymerization and bulk polymerization is 30 ℃～90 ℃, time is 0.05～10.0 hour, pressure is 0-4MPa, be specially 0.5-3.5MPa, described pressure is not 0; Or,

Described step 2) in, the temperature of described slurry polymerization and polyreaction is 50 ℃～120 ℃, and the time is 0.1～10.0 hour, and pressure is 0-4MPa, is specially 0.5-3.5MPa, and described pressure is not 0.

8. according to the arbitrary described method of claim 4-7, it is characterized in that: described method also comprises the steps: in described step 1) before slurry polymerization or bulk polymerization, in reaction system, pass into hydrogen; Or,

The add-on of described hydrogen is the 0-0.5% of described propylene monomer quality, is specially 0-0.2%, and the add-on of described hydrogen is not 0; Or,

Described method also comprises the steps: in described step 2) before slurry polymerization or polyreaction, in reaction system, pass into hydrogen; Or,

The add-on of described hydrogen is the 0-5.0% of described alhpa olefin gross weight, is specially 0-0.5%, and the add-on of described hydrogen is not 0;

Described method also comprises the steps: in described step 1) before slurry polymerization or bulk polymerization, be R to adding general structure in reaction system _4-nsi (OR ') _nexternal electron donor; Described R _4-nsi (OR ') _nin, the integer that n is 1-3, R and R ' are all selected from least one in alkyl, the cycloalkyl of C5-C10 and the aryl of C6-C10 of C1-C8; Or,

In described external electron donor and described promotor, the mol ratio of aluminium element is 0.01-1.0: 1, be specially 0.1-1.0: 1.

9. according to the arbitrary described method of claim 4-8, it is characterized in that: described step 1) and 2) in, described organic solvent is all selected from least one in the alkane of C5～C10 and the aromatic hydrocarbon of C6-C8, is specifically selected from least one in heptane, hexane and toluene.

10. in the polypropylene that the arbitrary described clay of claim 1-3 strengthens, alloy is preparing the application at least one in material for vapour vehicle component, wrapping material, barrier material, fire retardant material, appliance material, material of construction and daily life.