Process for preparing chlorine- and phosphorus-containing complex compounds

专利摘要:
Novel salt-like compounds adapted to be used as component of catalytic systems in the polymerization of ethylenically unsaturated monomers are disclosed: these compounds are obtained by reacting halides of transition metals or of aluminium with halides of alkaline earth metals, in the presence of phosphorous oxide derivatives which have the function of solvating agents. Also oxyhalides of transition metals lie within the scope of the invention.
公开号:SU1071223A3
申请号:SU802874602
申请日:1980-01-07
公开日:1984-01-30
发明作者:Греко Альберто；Бертолини Гульельмо；Пазьенца Джанфранко
申请人:Аник С.П.А.(Фирма)；Снампрогетти С.П.А. (Фирма)；
IPC主号:

专利说明:

ND
to
oo
This invention relates to a process for the preparation of new complex compounds formed by the interaction of chlorides or oxychlorides of transition metals or aluminum chloride with alkaline earth metal chlorides solvated by derivatives of phosphorus oxide, of the general formula
,;
2+
Ml.J
(Y)
where B ce2 (x .. ,, or cg (L,
2y + x - valency m;
M Ti4 +,,, Mo, Fe or
y O or 1, when x-takes the value providing the most stable configuration for metal M with ligand L or oxygen; L POCgj or CfcHjPOCe,
L ce or SbNd-Rose;
m Be2 -, - MD2, - Ca, Sr, and - coordination number M.
These compounds can be used as a component of catalytic systems for the polymerization and copolymerization of olefins.
The greatest use in the polymerization of olefins is found in the Ziegler-Natta catalytic system Clj,
However, this system does not allow obtaining low-density polyethylene and limits the structure of the polyolefins obtained.
The purpose of the invention is to obtain new complex compounds of the general formula 1, allowing to obtain polyolefins of various structures.
The goal is achieved by the fact that according to the method for producing chlorine and phosphorus-containing complex compounds of general formula G, a transition metal chloride or oxychloride of a transition group or aluminum chloride is subjected to interaction with an alkaline earth metal chloride at a molar ratio of 0.13-15: 1 in the presence of or C Hj- POCe at 120-140 ° C.
The resulting products can be used as a component of catalytic systems for the copolymerization of unsaturated compounds; for the preparation of copolymers of ethylene and alpha olefins, in particular those containing b and more carbon atoms, as well as for the preparation of low density polyethylene; for the copolymerization of ethylene with conjugated dienes, in particular, with butadiene, as a result of which copolymers containing unsaturated bonds are formed, which can be vulcanized with sulfur even at very low levels of unsaturation. Ethylene homopolymers can also be produced.
In this case, using a carrier, you can adjust the molecular weight distribution in order to obtain, for example, polyethylene or copolymers of ethylene and alpha-olefins, 5 which can be used for injection molding, you can also get homo-and copolymers of cycloolefins, copolymers of higher homologues, ethylene and dienes, and copolymers of various alpha-olefins.
The polymerization reactions are carried out according to known methods, if necessary in the presence of a reaction medium consisting of an aliphatic or aromatic hydrocarbon, the catalyst is formed by a mixture of one of the aforementioned compounds and an organometallic compound of a metal belonging to one of the first
Q three groups of the periodic system of elements. The reaction temperature ranges from -70 to + 200 ° C, as well. pressure can be either atmospheric or pressure at which monomer
5 react, or induced from the outside.
The molecular weight regulation can be carried out by known methods. One or more salts can be used (together with a solvent, such as), which are appropriately applied to an inert carrier, such as polythene, polystyrene or polyacrylic resins, alumina, etc. In that
In the case of polymerization, the use of an inert nip to regulate the morphology of the polymer obtained and, in some cases, the molecules, the equilibrium distribution
0 One of the advantages of the invention is that the catalysts are soluble in apolar solvents () and, therefore, can be supported on any carrier.
5 by the dry method (i.e., without using an aqueous medium).
Examples 1-8. Synthesis of compounds formed as a result of the interaction of a transition metal chloride or oxychloride of a transition group or aluminum chloride with the chlorides of metals containing talts of a solvated alkaline earth metal cation. General method of obtaining. The required amount of chloride
5 alkaline earth metals, TiCE and ROSE are placed in a 250 ml flask equipped with a connecting tube with a nitrogen source, a reflux condenser and a magnetic bar stirrer. The contents of the flask are heated with stirring to the refluxing temperature {120 ° C). The reaction is continued for the required time. When cooling to kom-:
At 5 watts, iskomogr crystals are formed. products that are used for PX analysis and separated within 10-20 hours. In the case of C HjPOCe, the temperature rises to.
As described, various experiments were carried out, the results of which are shown in Table 1.
PRI me R s 9-15. In the general case, an excess amount of MDce is placed in a cup made of agglomerated C-3 glass, together with a transition metal chloride or. The cup is loaded into a small extract of Kumagawa (with a capacity of 100 ml) located on a flask with a capacity of 150 ml, which contains the necessary amount of POS.
The system is refluxed until the transition metal chloride is completely removed from the cup. The crystals of the desired salt are separated by nonnocpieflCTBeHHo in a flask with slow cooling. In the case of Tice, the transition metal chloride is used as a solution in Rosy.
In accordance with the described, several experiments were carried out, the results of which are given in Table 2.
Polymerization of the considered unsaturated compounds (Examples 16-35) is carried out by loading 1000 ml of a solution of olefin in i-heptane and / or monomer and 4 mol tri butyl aluminum in this order in a 2 l steel autoclave, equipped with a stirrer and a set of thermostats, which provide temperature.
Hydrogen is then fed to the autoclave, if one is used, an olefin until the required pressure is obtained. The experiments are interrupted by the addition of 5 ml of isopropanol, the polymers are dried at 50 ° C under vacuum until constant weight is reached.
PRI me R, 16. Ethylene / 1-hexane copolymer; 0.089 mmol Ti according to Example 2 (Table 1), 1.9 mol of 1-hexene, 2 atm Hj and 10 atm of ethylene, the polymerization time is 1.5 h.
The output of the copolymer Cj / 1-hexene 320 g, the melt index MF 2,160, 67 g / Yumin; MF 21.6 / MF 2, at a concentration of Ti of 13.3 hours per m
Real density is 0.9420 g / mp; Cg 0.6 ml.%; Vs (cut-off speed) 48p dynamic impact (IZOP) j / ra 314; yield strength of 15 MPa; ultimate tensile stress 29 MPa; elongation of 771%; modulus of elasticity 490 MPa.
Example 17 Polymerization was carried out in the presence of mmol of Ti (Table 1, Example 1), 3.92 v K) nb 1-hexane, 0.5 atm Nd and
10 ATM SuP .; polymerization time 1h.
Yield 230 g C2 / 1-hexene copolymer, MF 2.16 0.91 g / 10 min; MF 21.6 / MF 2, at a concentration of Ti 18, .4. per million; real density 0.9107 g / ml; C, 1.2 mol.%; the copolymer is not destroyed by dynamic action; ultimate tensile stress of 21 CR;
elongation of 752%; elastic modulus
170 MPa
Example 18; The polymerization is carried out using 0.065 mmol of Ti (Example 2, Table 1),
3.71 mol of 1-hexene, 1 atm AND and
10 atm for 2 hours. At the end of this time, the autoclave tap is opened to provide an ethylene pressure of 2 atm, after which the reaction continues for another. 2h
260 g yield of ethylene / 1-hexene copolymer; MF 2, 47 g / 10; MF 21,67IF 2, at a concentration
Ti 12 ppm, Cf, 1.45 mol%; real density 0.9073 g / ml; copolymer does not break upon impact; pre-stress tensile stress of 17 MPa; elongation of 771%; module
elasticity 490 MPa.
PRI me R 19. Copolymerization of ethylene and 4-methyl-1-pentene. Copolymerization. performed using 0.062 mmol of Ti (Example 2,
Table 1), 3.25 mol of 4-methyl-1-foam, 1 atm Hj and 10 atm of ethylene for 1 hour.
240 g of ethylene / 4-methyl-1tpentene copolymer are obtained; MF 2, 053 g / 10 min; MF 21.6 / MF
2, with a Ti concentration of 12.3 ppm; real density 0.9271 g / ml; C 1.0 mol.%; the polymer does not break upon impact; yield strength of 13 MPa; ultimate tensile stress 28 MPa; elongation of 590%; elastic modulus of 432 MPa.
PRI me R 20. Copolymerization of ethylene and butadiene
polymerization is carried out at
using 6.066 mmol Ti.
(Example 2, Table 1), 0.76 mol 1.3butadiene, 2.5 atm of hydrogen and 10 atm of C2H4 for 2.5 h. Yield of C2 / SL copolymer 122 g; MF 2.16
0/14 g / 10 min; MF 21.6 / MF 2 ,,:: At a concentration of Ti of 25.6 ppm.
A polymer containing 1.8 wt.% Of materials extracted in acetone at ambient temperature has a total saturation of 0.4 mol.% (In terms of C) with an unsaturation ratio of 1.4-trf / vinyl equal to 3.
The residual polymer powder, .-, obtained at the stage of extraction with acetone (100 parts by weight), is homogenized using zinc oxide {5 hours), stearic acid (1 parts 2.2-methylene-5s {4-methyltributylphenol) (1 hours ), tetramethylthiouramyl disulfide (0.5 h.) and sulfur (3 h.) and vulcanized under pressure at 180 ° C for 30 minutes.
After vulcanization, the ethylene-butadiene copolymer contains 30% of material that is not extracted by boiling xylene (gel%).
Example 21 Ethylene and butadiene are copolymerized using 0.07 mM Ti. (Example 2, Table D), 0.15 mol of 1,3-butadiene, 4 atm H and 11 atm of ethylene.
After 4 hours, the autoclave discharged 210 g of the copolymer, MF 2.16 0.22 g / 10 min; MF 21, b / MF 2, at a concentration of Ti 16 h, per million
A polymer containing 2.2% by weight of material extracted in cold acetone has a total non-abundance of 0.88 mol.% (In terms of C) with a ratio of 1.4-trans / vinyl non-ablation of 3.2.
When the residue of the extract in acetone of this copolymer is subjected to vulcanization using the same materials and under the same conditions as in Example 20, the gel% is 65%.
PRI me R 22 o Homopolymerization of ethylene
0.051 mmol Ti (Example 6, Table 1) in the process of polymerization of ethylene at 3 atm of hydrogen and 10 atm of ethylene. After 6. h, 96 g of polythene are obtained, MF 2.16-0.036 g / 10 min; MF 21.6 / MF 2 ,, Ti. Concentration of Ti 25.4 ppm
Example 23. 0.096 mmol of Ti (Example 5, Table 1) is used in the process of polymerization of ethylene at 2.5 atm of hydrogen and 10 atm of ethylene. After bh, 345 g of polymer is obtained, MF 2, 22 g / 10 min; MF 21.6 / 2, at a concentration of Ti
13.4 ppm
PRI me R 24. Homopolymerization of ethylene on the carrier.
Polystyrene resin (XAP-2, the company Room and Haas, 300) is crushed and sieved, and a fraction with a particle size of 38-53 μm is taken. This fraction is subjected to "purification at the Soxhlet plant by extraction with metal, dried for at least 48 hours in P under constant vacuum, and finally degassed under dynamic vacuum and maintained under nitrogen atmosphere.
This resin (1.09 g) was suspended in CH2C € (25 ml), the compound according to Example 15 of Table 2 was added (0.0528 g, 5 wt.%) And stirred for 30 minutes with ambient.
temperature Then, the compound according to Example 3 of Table 1 (0.125 g 12 wt.%) Is added and stirring is continued for another 30 minutes.
The resin / gray) is evaporated to dryness under vacuum. The powder has a calculated Ti content, namely, 0.55 wt.%. 0.082 mmol of Ti deposited on this material is used in an experiment involving polymerization at 3 atm of hydrogen and 10 atm of ethylene.
After 6 hours, get 370 g of polythene, MF 2., 20 g / 10 min; MF 21.6 / MF 21, theoretical density 0.29 g / ml; the polymer is a flowable material with a cutting speed of 4 s, with 90% of the particles having an average size of 100-600 m with a Ti concentration of 10.6 ppm.
Example 25. A politically pulverized powder (1.2 g with an average particle size of 65-80 µm.) Was suspended in CH2Ce and the compound of Example 2 of Table 1 was added (0.158 g of 11.5 wt.%). Slurry suspension-,. for 30 minutes at ambient temperature, after which,. removed under vacuum.
The titanium content is 0.53 wt.% 0.075 mmol titanium thus obtained is used in the process of polymerizing ethylene with 4 atm of hydrogen and 11 atm of ethylene.
After 3.5 hours, 370 g of polina is obtained, MF 2, 31 g / 10 min, MF 21.6 / MF 2, with a titanium concentration of 9.8 ppm. The polymer is a flowable material with a shear rate of 5, moreover, 70% of particles have an average size of 100-600 m
Example26. The resin of Example 24 (1.80 g) was suspended in, (20 ml), treated for 30 minutes at ambient temperature and 0.225 g of the compound from Example 2 (Table 1) was added. Stirring is continued for another 30 minutes at the same temperature. The solvent is removed in vacuo, whereby a colored-violet powder containing a calculated amount of titanium, 0.68% by weight is obtained. 0.128 mmol of the titanium thus obtained is used in the process of polymerizing ethylene at 3 atm of hydrogen and 10 atm of ethylene.
After 6 hours, 430 g of polythene are obtained, MF 2, 45 g / 10 min; MF 21.6 / MF 2, with a titanium concentration of 14 ppm. The resulting material is a flowable product (cutting speed 4 s), with 80% of the product having an average particle size of 100-600 microns.
H: Polymer 27. Polymerization of cycloolefins.
1 ml of the solution from Example 12 in chlorobenzene (0.406 g in 25 ml) (2.75 mg W) was added to a solution of Ti Ba (0.25 ml 1 mmol) in cyclopentene (5 ml), while stirring.
After 4 hours with stirring at the same temperature in ethanol. 1.8 g (47% yield) of double-bonded polycyclopentamer, which has a mainly transstructure (81.3 mol%), is coagulated. Residual unsaturation consists of cis-double bonds (18.7%).
Example 28. 0.08 g of the compound of Example 9 is added to a solution of Ti Ba (0.25 ml, 1 mmol in cyclopentbne (5 ml), cooled to, with stirring. After 2 hours in methanol, 0.45 g is coagulated (yield 12.5%) of polypentenamer with mainly cis -bathing (78%). Residual unsaturation consists of trsins-double bonds (12%)
P p and 29. Copolymer of propylene and butadiene.
15 cm of 1,3-butadiene, 15 cm of prpilene, 3 mm of De (i-hexyl) 3 and 0.312 g of the compound from Example 2 are dissolved in this order in 20 ml of toluene. The solution was stirred at -20 ° C for 16 hours, and then 0.5 g of Cj / butadiene copolymer coagulated, the content of butadiene being 73 mol% (NMR H results: signals at 0.8 and 1.2 ppm). for propylene; 2.0, 5.0, 6.35 ppm for butadiene; solvent CDCB, reference standard GMCC).
Example 30. Polymerization of 1-mission ..
H -1-Decene (10 g) was mixed with g of the compound of Example 15 in methylene chloride (5 ml) at 50 ° C for 4 hours in a small steel reactor. The reaction is terminated by the addition of isopropanol. The product is taken up in methylene chloride (100 ml) and washed several times with 0.1 N. aqueous hydrochloric acid solution, aqueous hydrochloric acid solution and, finally, water. This solution is dried over CaCP and filtered, and CH2C62 and unreacted 1-decene are removed under vacuum of 0.1 mm at (b h).
Residue It has a weight of 6.5 g (yield 65%) and a viscosity of 30.5 cSt at.
PRI mme 31. A mixture of two different products on the carrier.
160 mg of the compound from Example 15 (Table 2) in 50 ml was added to the resin that was used to prepare the catalyst in Example 24 (fraction 75-150 µm, 1.75 and the mixture was stirred at ambient temperature for 1 hour.
182 mg of the compound of Example 7 (Table 1) is added to the resulting mixture and stirring is continued for another 30 minutes at ambient temperature. Then remove
under vacuum. The product thus obtained contains Of28% titanium, 0.1000 g of this product is used in the polymerization process,. identical to the process of example 24. Obtain 250 g of polythene, MF 2, 0 g / 10 min MF 21.6 / MF 2, with a titanium concentration of 11.2 ppm, and 95% of the particles have an average size of more than
200 microns, calculated density
0.3 g / ml The product is a flowable material (5 seconds).
PRI m e p32. 171 mg of the product from Example 15 and 225 mg of the product from Example 1 were added in this order to the same resin as used in Example 24 (fraction 75-150 µm, 1.80 g) in methylene chloride under the same conditions as and
in Example 31, resulting in a product containing 0.60% titanium. 0.950 g of this product is used in the polymerization process, which is identical to the process of Example 24, resulting in the formation of 290 g of polythene, MF 2, 017 g / 10 min; MF 21.6 / ML 2, with a titanium concentration of 19.7 ppm, with 90% of the particles having an average size of more than 200 μm, the calculated
density 0.33 g / ml. The product is a flowable material (4).
Example 33. The product from example 14 (210 mg) and from example 1 (200 mg) are added to the same resin
as used in example 24, (Aracci 75-150 µm) 2.0 g CH2Ce2p under the same conditions as described in example 31, resulting in a material containing 0.35%
titanium.
0.110oV of this product is used in a polymerization process identical to that described in Example 9, resulting in the formation of 170 g of polyethylene, MF 2, 07 g / miC MF 21.6 / MF 2, with a titanium concentration of 22 ppm. , more than 94% of particles have an average size of more than 200 microns, the calculated density of 0.32 g / ml. The product is a flowable material (5).
For example 34. cC-AugS. (bohemian) is kept at 700 ° C for 20 hours, and then 10 g of it is treated with Tice (60 ml) at 140 ° C (def egmirovaie) for 2 hours. After filtration, the content of titanium in ° C-AB (is 1, one%.
4.35 g of eL ht20i is treated with TiCEj. suspended in 15 ml
  1.20 g of product 3 is added (Table 1). The suspension is vigorously stirred for 30 minutes at ambient temperature and then the CH 2 is removed under vacuum. The final product contains 1.5% titanium,
122 mg of this product is used in the process of polymerization of ethylene with a partial pressure of hydrogen of 11 atM and a partial pressure of ethylene of 9 atm in 0.5 l of heptane for 2 hours, resulting in 78 g of polythene, MF 2, 25 g / 10 min; MF 21, b / MF 2, with a titanium concentration of 25.5 parts per million
Example 35. The same rf-AP Oj material (10 g) as in Example 34 is dried for 24 hours and then fluorinated with (1.0 g) at 600 ° C for 4 hours. This product (5 g) with a fluorine content of 1.2% is suspended in (50 ml) and stirred vigorously for 90 minutes at, then washed and dried under vacuum.
In .. the result of the analysis found that the product contains 1.6% titanium and 4.1% chlorine.
This material (4.35 g) is suspended with (10 ml) together with the product 3 of Table 1 (1.2 g) and the mixture is stirred vigorously for 60 minutes at ambient temperature. It is then removed under vacuum, as a result of which a product is formed, having the following composition,%: titanium 2.6; magnesium 0.66; chlorine 16.74
410 mg of this system, TiBa (8 mmol), n-heptane (1000 ml) and 1-hexene (25 ml) are used in a polymerization reaction for 2 hours at 13 atm of hydrogen and 9 atm of ethylene.
whereby 120 g ethylene / 1-hexene copolymer, MF 2, is formed,; 20 g / 10 min; MF 21.6 / MF 2.16 104 at a titanium concentration. 99 ppm, density 0.958.
 EXAMPLE 36. The same product jO -AfgO as in Example 34 (South) is treated for 2 hours and then sulphurized with concentrated sulfuric acid at, resulting in a material with a sulfur content of 1.5%. . This material (5 g) is suspended in Tlcl (30 ml) and then stirred in t @ h for 1 h at, as a result
5, a product is formed which, after being washed with a hydrocarbon and dried under vacuum, contains 1.2% titanium and 3.7% chlorine. This material (4.50 g) is suspended in CHjCt (10 ml) together with product 2 of the table, 1. The resulting mixture was stirred for 60 minutes at ambient temperature, after which the CHjClfj was removed under vacuum, resulting in an image;
5 with the material of the following composition,%: titanium 2.0; magnesium 0.60; chlorine 12.8. 430 mg of this material at 13 atm of hydrogen and 8 atm of ethylene together with a solution of 8 mm / l T1Ba and N-heptane. give 210 g of polythene for 3 hours, MF 2.16 0.11 g / 10 min; MF 21.6 / MF 2, when the content of titanium i is 41 ppm.
The proposed method makes it possible to obtain complex compounds of the general formula I, which can be used as a comnoHieHT catalytic system, which makes it possible to obtain polyolefins of various structures.
Table
 25
(0) CE2 35
50 45
dew
VERSAY2
21
Irl
MDS (
10.6 2.1 5 2.1 2 10
CaCiy
2
 Continued table. one
Continuation of table 1
x2 +
2 () -. (Beb4G mol. Weight. 1381
(TiCByL) - (, mol. Weight. 2035
2, 2t
(,,) - (MgLg) 4 mol. Weight 1703
(TigCe g) 2- (CaLa) 2, mol. Weight. 1719
(TiCEy-DJ (CaLa) 2+, mol. Weight. 2441
{T12Se d) 2- (SrLg) 2, mol. 1767 Note ,.
Continued table. one
T a 6 l and c a 2 Product properties: 1 - yellow flakes, mp, 12b-8 ° С; 2 - yellow prisms, mp, 124-5 с 3 - yellow prisms, decomposition at 170 ° С; 4 - yellow prisms, decomposition at 145 ° С; 5 - yellow crystals, so pl. 132-5С; b - yellow prisms, so pl. 155-B; 7 - yellow crystals, m.p. 150-2 C; 8 - emerald green needles. Note.
Continued t abl., Product characteristics: 9 - yellowish-brown prisms that become green at, so pl. 210-14C; 10-- green prisms, so pl. 208-10 C; 11 - green needles, so pl. lOS-lS C (turn brown); 12 - red crystals, so pl. 230-3 Cr 13 - gray-yellow flakes, decomposition at 14 - gray-yellow scnoni H, so pl. 240-5 C; 15 - colorless needles.

权利要求:
Claims (2)
[1]
METHOD FOR PRODUCING CHLORINE AND PHOSPHORIC CONTAINING COMPLEX COMPOUNDS of the general formula
Κ <> ₂ /] ² > ₂ Λ where B = «2 (χ + ί) or cg _{(x + 1)} L ';
[2]
2y + x is the valency of M ';
_m '_ T14 +, Mo ⁶ *, W ⁶ *, MO ⁵ *, Her ³⁺ or Ab ⁹ *, y = 0 or 1, when x assumes the value that provides the most stable configuration for the metal M ¹ with ligand L or oxygen;
L = POC b, or C ^ H ^ POC ^;
L '= Ct C _s NsR0Se or _2;
M = Be ^if , Mg, Ca ^z *, Sr ² *;
Z - coordination number Μ, characterized in that the chloride or oxychloride of a transition metal or aluminum hroristy reacted with an alkaline earth metal chloride at a mole ratio of 0,13-15: 1 in the presence of dew or C / ^ NeROSo at 120-140 ⁱⁿ S. ²
1071223 A

类似技术:

---

公开号 | 公开日 | 专利标题

---

SU1075949A3|1984-02-23|Catalyst for polymerization of alpha-olefins

---

US4013823A|1977-03-22|Process for preparing elastomeric copolymers of ethylene and higher alpha-olefins

---

US5563313A|1996-10-08|Immobilized Lewis Acid catalysts

---

US4105609A|1978-08-08|Deactivation of catalysts of the ziegler type used for the preparation of polyethylene in high pressure, high temperature processes

---

US4017525A|1977-04-12|Tetra| zirconium

---

SU578008A3|1977-10-25|Method of preparing polyolefins

---

SU1071223A3|1984-01-30|Process for preparing chlorine- and phosphorus-containing complex compounds

---

SU589929A3|1978-01-25|Method of preparing rubber-like copolymers

---

EP0222504B1|1990-02-07|Solution process for the preparation of polymers of alpha-olefins

---

EP0066204A1|1982-12-08|Polymerization process with chromium oxide on silica catalysts

---

US4537870A|1985-08-27|Polyolefin polymerization process and catalyst

---

JPH07650B2|1995-01-11|Method for producing catalyst component for olefin polymerization

---

US3669945A|1972-06-13|Process for producing a homopolymer or copolymer of ethylene with novel catalyst

---

EP0528908B1|1995-11-08|Olefin copolymers

---

HU215473B|1999-04-28|Process for producing solid catalyst for stereospecific polymerization of alpha-olefins and the polymerization of alpha-olefins with its application

---

CA1215962A|1986-12-30|Polyolefin polymerization process and catalyst

---

CA1043763A|1978-12-05|Catalyst and process for the polymerization of ethylene and therminal olefins

---

US4892852A|1990-01-09|Transition metal composition

---

KR920006446B1|1992-08-06|Catalyst component and catalyst for the polymerization of ethylene with alpha-olefins

---

Santarella et al.2000|Cationic polymerization of dienes III. Polymerization of 1, 3-pentadiene initiated by ferric chloride in hexane

---

US5180702A|1993-01-19|Metal halide catalyst, method of producing the catalyst, polymerization process employing the catalyst, and polymer produced by the polymerization process

---

GB2046766A|1980-11-19|Titanium trichloride catalyst component

---

US4182816A|1980-01-08|Olefine polymerization process

---

US4154702A|1979-05-15|Polyolefin catalyst

---

US4008359A|1977-02-15|Chrome catalyst

同族专利:

---

公开号 | 公开日

---

CA1159224A|1983-12-27|

---

IE800027L|1980-07-08|

---

IL59062A|1983-09-30|

---

US4304729A|1981-12-08|

---

LU82065A1|1980-08-08|

---

DE3000488A1|1980-12-04|

---

JPS5595623A|1980-07-21|

---

SE8000077L|1980-07-18|

---

GB2045261B|1983-08-03|

---

IT7919124D0|1979-01-08|

---

IT1110285B|1985-12-23|

---

HU182682B|1984-02-28|

---

DD148343A5|1981-05-20|

---

ES8100308A1|1980-11-01|

---

AU537984B2|1984-07-26|

---

ES487778A0|1980-11-01|

---

BR8000084A|1980-10-07|

---

AR223860A1|1981-09-30|

---

JPS644972B2|1989-01-27|

---

BE881041A|1980-07-08|

---

ZA8069B|1980-12-31|

---

SE445730B|1986-07-14|

---

AU5429680A|1980-07-17|

---

NO794308L|1980-07-09|

---

YU3280A|1983-06-30|

---

IL59062D0|1980-05-30|

---

YU40383A|1983-10-31|

---

GB2045261A|1980-10-29|

---

NO156564C|1987-10-14|

---

FR2445815B1|1985-03-08|

---

FR2445815A1|1980-08-01|

---

DK880A|1980-07-09|

---

PT70668A|1980-02-01|

---

DE3000488C2|1983-11-24|

---

NL8000105A|1980-07-10|

---

NO156564B|1987-07-06|

---

CH647785A5|1985-02-15|

---

RO80793A|1983-02-01|

---

YU40864B|1986-06-30|

---

IE49352B1|1985-09-18|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

FR3675M|1963-07-18|Rolland Lab A|Sodium eucalyptol sulfonates.|

---

US4206133A|1972-02-03|1980-06-03|Monsanto Company|Reaction products of metal oxides and salts with phosphorus compounds|

---

US4133823A|1975-02-28|1979-01-09|Monsanto Company|Reaction products of metal oxides and salts with phosphorus compounds|US4524195A|1983-10-19|1985-06-18|Phillips Petroleum Company|Process and catalyst for olefin polymerization|

---

US6777533B2|2001-12-21|2004-08-17|Basf Corporation|Production of polyetherols using aluminum phosphonate catalysts|

---

US20060183882A1|2001-12-21|2006-08-17|Dexheimer Edward M|Continuous process for preparation of polyether polyols|

---

US7226988B1|2001-12-21|2007-06-05|Basf Corporation|Method of forming polyetherols in the presence of carboxy-modified aluminum-based catalysts|

---

US6919486B2|2001-12-21|2005-07-19|Basf Corporation|Polyetherols produced using aluminium phosphonate catalysts|

---

US6706844B2|2001-12-21|2004-03-16|Basf Corporation|Polyurethane products produced from aluminum phosphonate catalyzed polyetherols|

---

US20060281894A1|2005-06-13|2006-12-14|Basf Corporation.|Method of forming polyetherols in the presence of aluminum phosphate catalysts|

---

US20060281892A1|2005-06-14|2006-12-14|Basf Corporation|Polyurethane products including aluminum phosphates|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

IT19124/79A|IT1110285B|1979-01-08|1979-01-08|COMPOUNDS OF HALIDE AND OXYLENE OF TRANSITION METALS OR OF ALUMINUM CHLORIDE WITH ALKALINE METAL HALIDE OF TERROSE, METHOD FOR THEIR PREPARATION AND USE|

---