JPS596206A - Production of acetylene high polymer - Google Patents

Abstract

PURPOSE:To produce an acetylene high polymer of a low catalyst residue content, by polymerizing acetylene by using a catalyst system obtained from a specified solid catalytic component and an organoaluminum or organoboron compound. CONSTITUTION:A solid catalytic component is obtained by copulverizing 0.02- 20mol of a compound containing at least one atom selected from the group consisting of Ti, V and Zr and a 1mol of a compound containing Mg at room temperature-250 deg.C for 5min-24hr in an atmosphere of an inert gas. Then, acetylene is polymerized at -80-150 deg.C in the presence of a catalyst sytem obtained by reacting or mixing the above solid catalytic component with an organoaluminum compound (e.g., triethylaluminum) or an organoboron compound (e.g., triethylboron).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes a novel catalyst system to achieve the small aggregation of acetylene in 1. The method for producing the 7-dilene high-temperature composite with +1'
′, spring resin material r, zircon material f]
Acetylene is produced using a catalyst system consisting of a solid catalyst component containing a Φ source r and a magnesium source r, and (Il) h-organic aluminum compound or organic boron compound 1' from the compound. A method for producing an acetylene high frL combination with 'J1' Ft,
In the short conversation ↑11, I would like to suggest that the acetylene high yield is reduced by using a catalyst system that is extremely high.

A catalyst component containing and having titanium/jI-J' and a catalyst component containing (1' aluminum) and (() from an arsenic compound) are known.

When acetylene is agglomerated using the catalyst system described in 1-, the polymerization activity of the catalyst system is extremely low. Therefore, after polymerization, the catalyst residue remaining in the polymer must be removed.
may cause deterioration of the polymer, or drying of the polymer may cause
This causes rusting of the equipment 6 used in the post-treatment process of polymers and the molding process of polymers or their compositions. Therefore, a process for removing catalyst residue is required. However, it is extremely difficult to remove the catalyst residue remaining in the acetylene+p polymer. On the other hand, there is a need to reduce construction and manufacturing costs by simplifying the process.

From C), it is important to remove catalyst residues after IR.
In other words, there are 9 imitators of the system that has a high degree of polymerization and +11.

(1) Therefore, as a result of various searches by non-inventors to solve this problem, (A) a small number selected from titanium raw materials, vanadium raw materials, and 0 and zircon raw materials. /I゛at least -f small element r and magnesilano, lj;), solid catalyst component 1' containing r:
t: r, Hini (I3) A7 ethylene is converted into 1 using a highly active catalyst system derived from Iso aluminum compound or Iso (Ikupo-Song compound).
The amount of catalyst residue is extremely small due to zero mixing.'/+: <
Therefore, the acetylene high 1n coalescence is easy to remove the catalyst.
l? ) and completed the present invention.

According to the present invention, the following effects can be achieved.

The IR synthesis activity of the catalyst system is high. Therefore, the catalyst can be easily removed and the catalyst removal process can be simplified. In addition, post-treatment of this polymer can significantly suppress rusting of equipment used in the secondary and molding processes.
゛It is possible to improve the quality of L to Onakabatake due to the poor quality of the molded product.

[
The origin of Φ1'(L'J, abbreviated as 1・'I゛1-If')
]1) and Magnesilano Hara J'. The final solid component is obtained by treating a compound with at least -(Φ) selected from a tetravalent titanium compound, a five-carrying vanadine compound, a tetravalent zircon f[', compound and a compound containing magnesium. ?1) During the treatment, titanium compounds, vanadine [
It is possible to treat only at least one compound selected from compound, zircon compound (other than 1-1-compound) and magnesium compound; R-donating compound is roughly treated,
? -) may be treated with a Tr compound. Alternatively, a Tr compound and a magnesilano\ compound each treated with an electrolytic compound and a magnesilano compound may be treated.

Magnesilla J, 11: The preferred compound is the following set [(1
) and (11)], the magnesium f[S
compound and magnesilano oxide, and magnesilan hydroxide lz f al.

Mg(ort')mx,',m(I)MgR,X
;,,n(If) (1)"Igoyohi(If)>I・Koyo, m is 0,1
Or 2, nizu J-18 or 2. R2 is water-4': Ijll, r soil 0' carbon zero is at most 16 aliphatic hydrocarbons (3, cycloaliphatic hydrocarbons and charcoal) (1=yJ<,j;1,
1. Kat-+ iI: Coal f splashed from y'3.14
hydrogen], 1, and X14♂ and X2 are halogen atoms r.

(1) Among the magnesium compounds represented by the formula, /(f
IC:: )4.Representatives of things 1+11 include magne, sium ethyra-1, magnezi-nj-futilato, j'1lii-ized magnezi-nno, '''1].Also, (11) Magryo/Uno, f shown by the formula
1′, as a representative example of compounds suitable for /xf (”
, butyl ethyl magnesila l\, dibutylmagnesium, ethyl magnesila l\r1'I l' % Kai
l'+-+reru.

In addition, the titanium compounds used to produce the solid [1 and 1 components] are fL compounds -C, which combine tetravalent titan with J-J; The proverbial four-valent σ
) Titanium 1 [: Agency 1 Narugagaagera) 3, T i (O
R")t is -t(Il+)(Also in the Ilti formula, e is 0 or ;, fat 111
”) from formula zero hydrocarbon and aromatic hydrocarbon 7-!-5/
From the 1st group, it is a hydrocarbon end group that has jumped out. X′ is”
rl // is an atom.

Among the tetravalent titanium compounds with the formula (1+l), Ii
Typical examples of f-kaburane are tetraethoxydikune,
Examples include tetrabuto-v-titanium, titanium fluoride, and titanium trichloride.

Furthermore, the vanadine compound used to produce the national catalyst component is a compound containing pentavalent vanadine. A typical example thereof is a vanadine (IS) compound represented by the formula (IVI).

vo(oR'), x, , (1~'')
0~) 2vC-Ogo, p is 0 or 1: 3
There is charcoal:! '=! , 1 is many and 7-J
From 12 aliphatic hydrocarbon groups, 1, alicyclic hydrocarbon groups and -)'j,, rl group hydrocarbon aqueous system /, L /ff
This is a hydrocarbon group selected from X” is HaIJ71
j, 'j' f. Among the five Hananone compounds represented by the formula q\'), representative examples of those suitable for bI' are:
Zircon compounds used to produce the solid catalyst component include tetravalent zircon. A typical example is the formula (\l) where /J<s11.

Examples include tetravalent zircon compounds.

Zr(OR') 9 Formula 1; is a hydrocarbon J< group selected from the group consisting of ÷hydrogen groups and 'Irh group hydrocarbon groups, and X' is a norogen atom. (Representative examples of suitable tetravalent dicon compounds represented by the formula include zirconium pytoxide, silconium nitrate, brobonyte,
Zirconia Ramuku [Koritoro・1. can be given.

In producing the solid catalyst component used in the present invention, the inorganic compounds and compounds described below are used. Compounds such as
It is a compound that has at least one idionic group, and is generally called a Lewis base. Typical examples of the electron-donating compounds include saturated or unsaturated aliphatic, alicyclic, or aromatic compounds as listed above.

Examples of such compounds include chain or cyclic ether compounds [charcoal Jl;, those having at most 24 fi; 1. r suitable. (For example, diethyl ether, di-n-methyl ether, seaisoamyl ether, anisole,
tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, ethoxyhenzene, diphenyl ether)], carboxylic acid-based 1z compounds [II with at most 18 carbon atoms; r'a (for example, benzoyl ( Rough acid, acetic acid, phosphoric acid) ], -I
f or Tasen 1 alcoholic compound or phenolic compound [Those with at most 181 carbon atoms are IfJ
m (for example, alcohol, n-゛tityl alcohol phenol, p-methylphenol, ethylene glycol)], the above-mentioned carbo 'J ri'? anhydrides of such compounds (e.g., acetic anhydride, phthalic anhydride, delinzoic anhydride)], Nisder-based compounds (e.g., alcoholic anhydrides) obtained from the above-mentioned carboxylic acid-based compounds and alcohol-based compounds or phenol-based compounds (11); Edyl sozoate, r-butyrolactone, f'i'fi #2 phenyl, p-ethyl vinegar, IV dibutyl benzoate, aldehyde compounds [those with at least 3 carbon atoms are suitable for QJ' ( For example, henzaldehyde ζ butyraldehyde, acrylaldehyde, cinnamaldehyde)], ketone f1; compounds [preferably those with a total carbon number of at most 24 (for example, a7tone, benzophenone, acetophenone, cyclohexanone) ], the above-mentioned carboxylic acid no-ride compounds (for example, Enzan), 11-benzoyl, odor (IS benzoyl, i fL; cyclohegylene carbonyl), carbon-1:; −, even 24 pieces of bow? Ester-based compound (even if υ
, tetramethylsilyrote, tetraethylsilyrote,
Tetracresyl silicate, trichloromethyl silino r
−))], mono or borishi “nohe・lean [all/,
I zero is at most I (1 (l n is Ir, 4
], amine compounds [total carbon number is at most 111
If) 1jl (for example, ←r, tributylamine dilyaniline)], amiF-based compounds [those with total carbon JC &9 of at most 36 are preferred (for example, N,
N-dimethylhenzamide, acetamide, N,N-
dimethylhexanoxamine I)], phosphoric acid ester compounds or phosphorous ester compounds (those having at most 24 carbon atoms are suitable (for example, triphenyl phosphite, diphenyl phosphorus, -,','Qr
'i-Light, Rin (5,2) IJ-r-Del, Rin (
S: 9゜tri-noenyl)] Right ゛ and ゛ are raised and A is done.

It's 11.1 juice (fl・l /1111, used to produce ingredients7, city f"f!','i゛1''
l (1'i'?& monsters) Among the monsters in 1, nothing (i'': (l', compound and 1.tekaku, 11'34 +1
．． The 11th table of the 11th table, the 1st group 11th to the
, l e(-1il(J'n ノ'Lto(1:) ha r
r saponified product), fiji f' sword number, Li nitrate,;
Song (1) 1゛Day 2'' 1X, 11, song nitric acid jλ1・1'
/1.I can't give up.

1iii Solid contact 1. Make the %l component 1.1/, -, first 15r (II combined tl'rito magefu, tsu 1.
fl:, ``Madoroi''
・As a method for processing these chemical compounds (hereinafter referred to as [compound method-1 and j (c) and・Method of contacting in a PI solvent or in the incompatibility of ai'i'+r+1'l solvent (1-lower (when the treated material is liquid) (hereinafter - [:
1-Contact method-1) Z1.

The milling method generally uses a milling machine such as a ball mill, a vibrating ball mill, an impact mill, and a colloid mill, and co-milling under an atmosphere of an inert gas (e.g. nitrogen 7 (≦, argon)). Just shift it.

It may be possible to take measures such as cooling, but this co-pulverization may cause corrosion.
In the case of (・1), it may be cooled for operational convenience. The time required for co-grinding can be defined as -IIl<-, depending on the performance of the grinding, etc.1.) However, it is essential to use a small amount of crushed material when using 11).

1!1 lane crushing! f'y is almost completely uniform 7 [shape 1;
It is preferable that C-shaped ζ1[; Therefore, the co-grinding time is generally 5 minutes to 2 minutes.
4 hours, 3 In addition, the contact fQl: method is in the presence of an inert solvent (II. or I. ).

The inert solvent used in this process is a dry solvent (with a water content of 1 kg), and representative examples include fats with a boiling point of 10 to 300°C, JIjj group hydrocarbon water (for example, tap', n-hexane, n-bebutane,
n-octane), fatty JvJ group hydrocarbons (even Q; 1゛, cyclohexane, dimethylcyclohexane), aromatic group hydrocarbons (!l: eha, toluene, xylene), and these hydrocarbons (For example, Q-1, 41: i, i carbonized hydrocarbon, trichloroethylene, chloride). In this contact force method (C), inert solution 1) Among the above-mentioned Tr compounds, electronic fJ1.-1j compounds, and magnesium compounds, at least one is in the form of a When the treatment capacity is XI, the treatment can be carried out in the presence of an inert solvent.

Also, contact) II, 1, degree is the A/class and proportion of the contact object, contact time XC et al. 0/ and other conditions! 11.
However, the normal temperature (20℃) or 2
5 (1'C) The contact time varies depending on the type and proportion of the contact material, the contact temperature, and other conditions, but
Generally, it takes 5 minutes to 2.1 hours.

Below 1. ft in both the co-grinding method and the contact method.
The ratio of Trt compound to +, 1 mol of magnesium compound is generally (1, (12 to 20 mol).

The solid catalyst component prepared as described in 1- below is treated in a treatment method using a commonly used inert solvent and treated with solid f4 (11.TrL remaining in the component; Compounds and electronic compounds (if used) are washed until the spatula is no longer visible in the cleaning solution.
In order to remove the used inert information) 15, L and N
It is desirable to make f'i, but if you do not use the electronics-lj chemical a 4 stool river, please do not use kana 1) It is not necessary to wash the sushi.
, ) 1, I.

'I''1 in the solid catalyst component obtained as follows I-
-))', 'j child's I, Fii is generally i/1:0
．． j and l in fl 1~:30 and contain magnesium atoms! -1F, 6:t (1, l~', 4 f
l This is section 1.1 of middle school.

It is used in the acetylene high-temperature medium of the present invention.
゛e Aluminum compounds or compounds (among the zero compounds, representative t1 compounds of organic aluminum compounds - general formulas are ten people [(Vtt formula, 10 formula and (VI + i)
AIRRR(~)1) R'Ie"' At 0-AI R" R12(
Vll)AI R,, At most 12 aliphatic, alicyclic or aromatic carbons (IL hydrogen group, halogen atom or hydrogen atom, at least one of which is the hydrocarbon group, E10, R", and R12 may be the same or different, and are the terminal groups of the hydrocarbon, RI'O+) iJ hydrocarbon, B< group, and X6 is
1; CJ'.

Among the 11 aluminum compounds, the number N I'l'J ('+: triethylaluminum uno\, trizo'j bilaluminium\,
Triglylaluminium 1, triglycylaluminino\mu''2'' trialkylaluminum such as cutylaluminiumuno\, diethylaluminum hydrite diisobutylaluminum, hydride, alkylaluminiumino 1 hydride and dief
Examples include aluminum chloride and diethyl aluminum bromide.

Further, among the organoaluminum compounds represented by the formula (11), typical examples include alkyldialumoxanes X(i) such as tetraethyldialumoxane and tetrabutyldialumoxane.

Furthermore, (~111) Ij machine aluminum Uno represented by the formula,
Among the compounds, ethylaluminum sesquichloride is a typical tC compound.

Further, the general formula of a typical organic phon compound is represented by the following formula [(IX)':l.

BRRR (IX) GX ) Formula K h ite, R1', RI', o. J:
HIR'' M may be the same or different types, and the number of carbon atoms is at most 12 aliphatic, alicyclic or aromatic hydrocarbon atoms, 1, 1, 2, 2, 2, 3, 3, 3, 4 atoms, At least one of them is the zero hydrocarbon group.

Representative examples of the organic boron compounds represented by the formula (IX) include trialkylboron such as triethylboron, tributylboron, and trioctylboron;
Examples include alkino-phoron hydride chlorides such as diethyl boron hydride and diisobutyl boron hydride.

In carrying out the present invention, the solid catalyst component is
A reaction product or mixture of an aluminum compound or an organic boron compound or a compound having an electron (J'.-fi property) may be introduced into the reactor separately, but two of them may be All may be mixed in advance.

Alternatively, it may be used after being diluted in advance with a hydrophilic solvent used as a solvent in the polymerization described later.

In carrying out the polymerization of the present invention, 1
(2) solid catalyst components and aluminium compound or a solid catalyst component; + Use of 'j'F thing 1
There is no limit on 411'', but I C+ +++g ~;,! per 1e of inert organic solvent used in polymerization;
+1 9 solid catalyst components and 001~] (1 0
The ratio of millimoles of organoaluminum compound/l- or organoboron compound used is preferably J'. In addition, the use of aluminum or organic boron compounds is,
The TrfILa compound contained in the 1b1 catalyst component [1
Generally, it is in the range of 1 to I000 times mole.

The polymerization temperature is generally -s (1°C to 150°C
It is.

In addition, there are no specific restrictions on the type of polymerization, the configuration of the polymerization reactor, the method of controlling polymerization, and the Shundokoro Misaki method, and all known methods can be applied.

The present invention will now be explained in more detail with reference to Examples. In each of the Examples and Comparative Examples, all the compounds used in the production of the solid catalyst component and in the 1R reaction were substantially free of moisture. Further, the production and assembly of the solid catalyst component were carried out in substantially no moisture and in a nitrogen atmosphere.

Example 1 City ft1. anhydrous magnesium chloride 5 (] , q (
(1.5 2 mol) and vanadyl butyrene zo9 (o
．． o: Umol) was placed in a vibrating ball mill container (cylindrical stainless steel, internal volume 17?, stainless steel pole with a diameter of 10 mm, approximately 50% filled by apparent deactivation). This A
1 to 1h, N':, 1. Kali 1ill, zu1. ,
By crushing Jl, i, F (11 Shimono 411, and 1, this crushed G Put fl, q into 911 Nolasco of HI4, add Heki'leaf I 00 m((1'
1'', : J'f L!t' was separated. Vanadyl phthalate was found in the iris solution and washing was repeated. -C
I'A,'t I',! - Te Inui II! By paying ¥4, you can get 1 powdery solid (Il il), 1 paste, 1 minute.
() 3, bar J-Jin 1 Emperor r() in this solid catalyst component
I) r4-self: 11 is in 10: +'C% Tea Tsuta.

1"S, Mouth I (1f Crow with Iku Ping Liu) published - Tokure-no ni Tono 1.2 "No wo 21) fl III/:
, 1σ) Solid 11 made using the Knob method /Iν, l+'5
Poor) I C・l, -ノ, l・Riedil Aluminum Uno% l
mt (8.7 mmol) was added and the ace-f-1/linka was heated for 11 minutes to 0.7 mm at -78°C. Il kg
/nn' for 2 hours. After a 2-hour hiatus, we released the mountain and valley scum and concluded the agreement.

This 1 compound was washed with IO (1 me) toluene and dried over 7 g H311C at 1% temperature. As a result,
3 g of powdered acetylene high polymer was obtained. The activity per vanadine f- is: oooy/,! There were 7 vanadine atoms.

Actual Example 2 In Example 1 (instead of the anhydrous J71ii compound Magene Cyrano\ used in A+, magnesiuno\cordilato 4, vanadyl phthylate glue 0 to 4Ii,, i fl
L titanium
The solid catalyst component was co-pulverized, washed and dried in the same manner as in step 1.71). This solid catalyst J & external middle titanium!
:J1. JF+: including r. was in the f and l sections of 2.

Add Heggy Rinn 20 to the A-top crepe used in Example J.
Add 0 ml: and add tributyl pox + me (4
Add 1.74 mmol of the solid catalyst component and stir the acetylene gas at a temperature of 30°C for 1 hour.
After evaporation, it was dried with warm H(p) at +'C.As a result, 4 g of powdered acetylene polymer was obtained.The activity per titanium atom was 20og/,! Ta.

Example 3 Co-pulverization was carried out in the same manner as in Example 2, except that zirconium butoxide was used in place of the titanium tetrachloride used in Example 2, and the same catalyst component was washed with an inert solvent. And so. This solid touch h~', 'l'V',
The content of /lucon atoms in the sample was: 0 sun, 38 city-shukuchi. In place of the tributyl boron used in Example 2, trisofudyl aluminum was used.
is exactly the same as in Example 2, with the same cleaning and dry inspection! Ruyu J"/"I53Q's powdered acetylene high 1 mouth combination 6, Jill" Hara J' AL RI (7) 71T
'l'l'1: (li, l: (0, q, /, tsujirunishi, original r de attu)).

Actual addition 11 rows 4 Ability 11 examples 2 "Koiri? Used, 4 ll'llj conversion 10, Tsunoganeri tetraptokinchikun 15. So (
The solid ftp11B medium component was 111 in the actual h1m Example 2 except that 14 mmol) was added. This is the same condition as Example 3, where ij<rY, fit
: (f' and *2,1) 6 g of powdered ace-f-rene Takaichi α form was obtained.Activity per titanium raw material r: 01, : + no, q/, !i' It was a titanium atom.

Actual htM 1 row 5 Actual MHj ('A) 1 co-pulverization 1! At 11, detraedyl silicate 1 n as an electro-donating compound
, q (o, o 4 moles) was used in Example 1
The solid catalyst component was mixed under exactly the same conditions as
'ff' and after drying and drying, 3, q powdered acetylene high i11 compound [(・1 (also.
The I activity of 2 n o , so/conovanadine +1; 1.
It was J''.

Add heptane to the II flask
(1fl IIIζ Magnesium Ezilate IO,
9 (87 mmol), tetrabutystitanium I 9 (
1 mmol) was added thereto and an I stroke was performed at 4' for 2 hours at 70°C. il, ), i', after separating the entangled solids by 41,
Use heptane to il' 7 ('j,
Jj Support r・Ka recognized'/'C<nai) Dimensions 614 purification Jj L, 3, this solid material 4 (1 of 1℃!
By drying with l'i'L Iα, a powdery solid catalyst component was obtained. Titanium raw material r- in this solid catalyst component
The content of ;IH, was ()5 tons (1:%), prepared in exactly the same manner as Example 3, washed and dried 11j
When f4 was carried out, 2 g of acetylene-rich polymer was obtained.

Activity per titanium atom: 0, 4 (l o 9 /
, 9-jitanhara-oka.

EXAMPLE 7
, diisoamyl needle mole) was added as a heptadyl compound, and the mixture was stirred at 50° C. for 4 hours. ? ()
After separating the isomorphs obtained, they were separated using heptane.
6L purification was repeated until titanium μ; 1r. was observed during the 11-hour test and the concentration became 1. By drying this solid at a temperature of 40°C, a powdery homogeneous substance (τL component?) is obtained.
)is. The content of titanium atoms in this solid catalyst was 111 and 1191; Example: Polymerization, 61L cleaning and dry SL were carried out in exactly the same manner as in Example;
2, 9 acetylene high polymerization books (France). The heptadonia per 1 liter of titanium was 200 g/l.

Ratio 1 bite example 1 Add 2 (1 (
l m(, 2.9 (5.8 mmol) of tetrabutoxytitanium, 7 mmol of triethylaluminum)
Add 3 (at a temperature of 1 °C, acedilene gas at partial pressure tl'.) kg. / (:+l+2 and polymerized for 2 hours. After 2 hours, the content gas was released to terminate the polymerization.

This polymerization product was prepared using toluene at room temperature.
R('i) Clean until no traces of dirt are detected.

Let's dry this same product at a temperature of 10℃.)
) 11 pieces of 3g of powdered acetylene takatori. The activity per titanium atom is 229/. It was Wachitan Haracho. Furthermore, 1 ton of titanium remained in the powdered acetylene polymer 111.

Special F-Cho Applicant Published by Showa Raijo Co., Ltd. Agent: Patent attorney Tate Kikuchi 35

Claims (1)

[Scope of Claims] (A) A solid catalyst component containing at least -f1 selected from a titanium raw material r, a vanadine raw material [and a zircon raw material -(+Jin
A method for producing an acetylene high ifi compound f4\ from a single compound (9', '1') using a catalyst system that uses a compound containing