JPS63113003A - End-modified propylene polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled polymer useful as a compatible solvent for polymers, surface improver for substances, viscosity index improver, drag reducing agent, etc., wherein the all polymer chains are modified with an oxygen- containing group only at the end groups and the polymer is close to a monodisperse state. CONSTITUTION:An end modified propylene polymer shown by formula I [R is divisible 1-8C alkylene; R<1> is H or group shown by formula II (R<2>-R<4> are 1-8C alkyl); n is 20-10,000]. The polymer, for example, is produced by polymerizing propylene in the presence of a polymerization catalyst consisting of a catalytic component containing a vanadium compound shown by formula III (R<5>-R$8 are H or 1-8C hydrocarbon) and an organometallic compound of a metal of group I-III of the periodic table to give a living propylene polymer, reacting the living propylene polymer with an alkylene oxide shown by formula IV (R<8> is H or 1-6C alkyl) and bringing the reaction product into contact with a proton donor or reacting the living propylene polymer with CO and bringing the reacting product into contact with the proton donor and then hydrogenating.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a propylene polymer terminally modified with an oxygen-containing group.

Conventional technology Polymers in which substituents such as functional groups are bonded to propylene polymer chains obtained by using a solid Ziegler-Natsume type catalyst are known, but substituents are selectively attached only to the terminals of the polymer chains. It is difficult to combine.

An object of the present invention is to provide a 7c1 pyrene polymer in which only the terminal ends of all polymer chains are modified with oxygen-containing groups and which is nearly monodisperse.

The present inventors had previously discovered that nearly monodisperse polypropylene could be obtained by living polymerization of propylene using a soluble vanadium thread catalyst. developed propylene polymers modified with hydroformyl groups and amino groups, respectively (Makromol, Gham, 1
86.

1825 (1985), Makromol, Oh
em,, Rapldcom+aun, 5, 811
(1984), Adu, Polym.

Sex, 75/74, 2ot (t986)].

The present inventors have an idea for providing a polymer obtained by the above method or in which the terminal of Bing polypropylene is modified with an oxygen-containing group such as 10H group or 10S L(R)s group. We conducted research and completed the present invention.

That is, the present invention has the following formula: is an integer, and R-R are the same or different alkyl groups having 1 to 8 carbon atoms. ] The gist is a decorated propylene polymer with terminal 1.

The terminal-modified propylene polymer of the present invention has the general formula [wherein R5-R8 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms]. However, at least one of R5-R8 must be a hydrogen atom, but not all of R5-R8 must be hydrogen atoms. ] A catalyst component containing a vanadium compound (al and Group 1 to Group I of the periodic table)
(1) When R1 in the above general formula of the terminally modified propylene polymer is a hydrogen atom, (I) ) A method of reacting with an alkylene oxide of the general formula [where R8 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms] and then contacting with a proton donor; or (reacting with c4 -carbon oxide and then contacting with a proton donor) A method of introducing an aldehyde group t- into the terminal of the polymer by contacting with A propylene polymer modified with a terminal OH group can be reacted with a silicon compound of the general formula 5IR2R5R'X (wherein R2-R4 have the same meanings as above, and X is a halogen atom).

A living propylene polymer is produced by polymerizing propylene in the presence of a polymer consisting of a catalyst component molecule al containing a vanadium compound represented by the following general formula and an organometallic compound (bl) of a Group 1 or Group I metal. obtained by the name.

General formula [However, R5-R7 have the same meanings as above. ] Among the vanadium compounds included in the above general formula, the following compounds are particularly desirable.

Furthermore, solid catalyst components in which these vanadium compounds are fixed to metal oxides such as silica may also be used. The solid catalyst component is prepared by, for example, reacting silica with a 710 silicon compound such as chloromethylphenethyltrichlorosilane, and then reacting the resulting solid product with an organic alkali compound such as sodium 1,3-butanedionate. , then by reacting the solid product with a vanadium compound.

Catalyst components (organometallic compounds of group I to group metals used with al (bl include organic compounds of lithium, magnesium, calcium, zinc and aluminum, in particular dimethylaluminum chloride, diethylaluminum chloride, An organoaluminum compound represented by the general formula R2A/XL such as diethylaluminium bromide and diisobutylaluminum chloride, where R is an alkyl group or aryl group having 1 to 8 carbon atoms, and X is a 10-gen atom. desirable.

In the living polymerization of propylene, in addition to homopolymerization of propylene, a small amount of ethylene or 1-butene, 1
It is also possible to polymerize in the coexistence of a-olefins such as -hexene and 4-methyl-1-pentene.

The polymerization reaction is preferably carried out in a solvent that is inert to the polymerization reaction and is liquid at the time of polymerization. Examples of such solvents include saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane, and heptane, cyclo Examples include saturated hydrocarbons such as propane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene.

The amount of the polymerization catalyst used in propylene polymerization is 1 x 10-' to 0.01 mol, preferably 5 x 10-5 x ILI-! of the vanadium compound per 1 mol of propylene or propylene and a small amount of comonomer. r mol, organometallic compound is 1 x 10 to 0.1 mol, preferably 5 x 10-
It is 5 to 0.01 mole. Note that the organometallic compound is preferably used in an amount of 5 to 25 moles per mole of the vanadium compound.

Living polymerization is usually 0.5 at -100C to +150C.
It lasts ~50 hours.

The molecular weight and yield of the living propylene polymer obtained can be adjusted by changing the reaction temperature and reaction time. By setting the polymerization temperature to a low temperature, particularly -30C or lower, a polymer having a molecular distribution close to monodisperse can be obtained.

-65C or less, )Jw (weight average molecular weight)/Mn
(It can be a living polymer with a number average molecular weight of 1.05 to 1.40.

A reaction accelerator can be used during the polymerization reaction. As a reaction accelerator, anisole, water, acid i, flucol (
methanol, ethanol, inglobanol, etc.), and esters (ethyl benzoate, ethyl acetate, etc.).

The amount of accelerator used is usually 0.1 to 2 mol per mol of vanadium compound.

By the above method, a nearly monodisperse or pink propylene polymer having a number average molecular weight of about 800 to about 400,000 can be produced.

The alkylene oxide to be reacted with the living propylene polymer has a general formula.Specific examples of this compound include ethylene oxide, propylene oxide, butylene oxide, and the like.

The reaction between the living propylene polymer and the alkylene oxide is preferably carried out by supplying the alkylene oxide to the reaction system in which the living propylene polymer obtained in the first step is present.

The reaction is carried out at -100C to +150C for 5 minutes to 10 hours, but it is preferable to carry out the reaction at a temperature close to the temperature of the living polymerization of propylene in the first stage.

Aluolene oxide is used in an amount of 1 to 1,000 mol per mol of the living polymer.

The reaction product of living propylene and alkylene oxide is then brought into contact with a proton donor to obtain the terminally hydroxylated propylene polymer of the present invention.

Propylene donors include methanol, ethanol,
Examples include alcohols such as phenol, and mineral acids such as hydrochloric acid and sulfuric acid. Alcohols and mineral acids may be used simultaneously.

The proton donor is usually used in large excess. Contact with the proton donor is typically carried out at -100C to +t QOC for 1 minute to 10 hours.

The terminal hydroxylated propylene polymer obtained as described above has the following general formula.

[However, R and n have the same meanings as above. ]

The reaction between the living propylene combination and carbon monoxide is carried out by supplying carbon monoxide, if necessary diluted with an inert gas or liquid medium, to the reaction system and maintaining the temperature at normal pressure. The reaction is carried out under pressure of -1UO1Z' to +IUOC'%, preferably at a temperature of -8ac to OC, for 5 minutes to 10 hours.

The subsequent reaction with the proton donor is as described above (1).
) is carried out in the same manner as in method (1). By doing so, aldehyde groups are introduced at almost all terminals of the propylene polymer.

The Mizutake reaction of a propylene polymer whose terminal end is modified with an aldehyde group is performed by converting the propylene polymer into LIA/H4, NaA/H4, LiBH4°Na, preferably in the presence of a solvent.
0.5~ with reducing agent such as BH4 and -5OC~+tooc
This is done by contacting for 10 hours. As the solvent, ethers such as cyclic ethers such as diethyl ether, dibutyl ether, cyamyl ether, cyfurkyl ether, and tetrahydrofuran are preferable.

By doing as described above, a terminal hydroxylated propylene polymer having the following general formula can be obtained.

OH3 (OH2-(H-), 0H2-OH [However, n has the same meaning as above.] The silicon compound to be reacted with the terminal hydroxylated propylene polymer and the silicon-terminated hydroxylated propylene polymer has the general formula SIRRRX [However, R2 -R
4 and X have the same meanings as above. ]. As a silicon compound, 5L (cH,)3cl! .

81(02H5), G/, 81(1-03H,)3(/
, 31(C4H2)3C1! .

51 (1-C4H5+)301! ,5Jc6H4,),
C/, 81(08H,7)3Cl.

5l(OH3), Br, 51(C2H5), Br, al
(OH,)2(C2H5)C/.

31 (OH3) (C2H5) 201! ,81(OH,)
2(03H,)C/.

Examples include s l(c Hs )(c 4 H9)20/.

The reaction between the polymer and the silicon compound is preferably carried out in the presence of pyridine at -50C to +100C for 1 to 10 hours. The silicon compound is contained in an amount of 1 to + per 1 mole of the polymer.
, 000 moles are used.

By doing as described above, a terminal oxysilylated propylene polymer having the following general formula can be produced.

O (When using the propylene polymer obtained by the method in 11 (a): and n have the same meanings as above.) ofm (When using the propylene polymer obtained by the method in 12 (b)) : has the same meaning as above.] The propylene polymer having the above general formula obtained as above has a number average molecule i( It has a very narrow molecular weight distribution (My/Mn=1.05-1.40) f (in terms of propylene), and almost all chain ends are modified with oxygen-containing groups.

Effects of the Invention The polymer of the present invention can be used as a compatibilizer for polymers, a surface modifier for substances, a viscosity index improver, a drag reducer, and the like.

The present invention will be explained below using examples. The characterization of the polymer was performed using the following equipment and method.

0) ('NMR analysis JEOL Ltd., CX-SOO, Fourier transform NMR spectrometer (5QOMh, room temperature, pulse interval 5.
0 seconds) and FX-100, Fourier transform NMR spectrometer (100 MHz, 1 room temperature, pulse interval 5.0
seconds) OGPC manufactured by Showa Denko ■, Shodex f, 0HT-3, Kölpermeation chromatography (column: Shokudex 80M, 14QC, solvent: O-dichlorobenzene) OIR analysis manufactured by JASCO Corporation ■, FT/IR- 3 Infrared Spectrophotometer Example 1 Toluene 301 was placed in a 30ON flask that had been sufficiently purged with nitrogen gas and cooled to -78C.

At the same temperature, millimole of propylene was processed and dissolved in toluene. Then 10 mmol of AI! (C2H5)2
C1! A toluene solution and a 1.0 mmol V(acetylacetonato)3 toluene solution were added, and polymerization was started with stirring. Polymerization of propylene was carried out at -78C for 1 hour.

Reaction with propylene oxide 74 mmol of propylene oxide was added to the above reaction system and stirred at -780 for 1 hour.Next, it was brought into contact with a 30ON hydrochloric acid-methanol mixed solution, and the resulting polymer was diluted with 5UOml of methanol. It was washed twice and dried at room temperature under reduced pressure.

The molecular weight of the obtained polymer was measured in Gpa, and the result was Mn
=+, 900 (Mw/Mn=t, 2).

In addition, when this polymer was analyzed by IR, it was found to be 3500Crr.
A broad peak due to absorption of hydroxyl groups was observed near r1.

Furthermore, the HNIJR spectrum of this polymer is shown in FIGS. 1 and 2, and the assignments are as follows.

0.7-1.7 Protons of polypropylene moiety 3.5 - CH-CH2-(a) 0H.

5.9 -0H2-OH-(b)CI(3 s, o + CH=C!(2(c)5.8
-0H=C)((di, 2 Molecule t (M
n) is 2,000, and this value is in good agreement with the Mn=+, 900 measured by APA.

Therefore, the obtained polymers are the following three types of polymers (1
) to (3), and judging from the area ratio of signal (al, signal (t)l, and signal tc+), polymer (2) and polymer (1 evening is 70% each) having a hydroxyl group.
mol% to 10 mol%, polymer with terminal double bond (31
was found to be 20 mol%.

CH3 CH3 CH3 CH3 4CH2-OH-)nOH2-(H= CH2f311
dl tel (The average value of n is about 45) Example 2 Living polymerization of propylene A 200 mt auto tank v- fully purged with nitrogen gas
7' was charged with toluene as a solvent and cooled to -78C. 35.9 (0.85 mol) of propylene at the same temperature
and dissolved in toluene.

Then 5 mmol of A/(C2)13)2CI! ) toluene solution and u, 5 mmol V(acetylacetonato)3 toluene solution were added, and polymerization was initiated at -78C.

The reaction mixture was then pressurized to 30 atm and stirred for 1 hour. After the reaction is completed, -carbon oxide gas is purged, -7
The reaction solution was poured into ethanol cooled to 80°C to precipitate the polymer.

The resulting polymer was washed five times with 5QQa6 ethanol and then dried. When the molecular weight and molecular weight distribution of the produced mourning polymer were measured, Mn = 4.400, MY /
It was a nearly monodisperse polymer with Mn = t, 2.

When the XR spectrum of the obtained polymer was measured,
An absorption spectrum at 1,725 cm due to carbonyl groups was observed, and it was recognized that carbonyl groups (aldehyde groups) were introduced into the polymer.

In addition, the number of molecules of carbonyl groups introduced per molecule of the polymer chain was calculated using the following formula: O Here, 41 and 440 are the molar absorption of 1,460 trn-1 caused by polypropylene, respectively. 1,723c! due to the coefficient and carbonyl group! Molar extinction coefficient of rr1, ^1723. At460 is 1,723-
and 1,461]crn, Mn is the number average molecular weight, and 42 is the propylene molecule tft.

As a result, the value of CO3 was 1.0, and it is clear that there is one molecule of aldehyde group per molecule of the polymer.

200 red three-necked 7-lasco K, LIA/H4 equipped with hydrogenation reflux condenser, dropping funnel and magnetic stirrer
A solution consisting of 31 mmol and diethyl ether 501+17 was introduced. To this solution, a solution of 85~ terminal-modified taclobyrene polymers obtained above with aldehyde groups and 15aj of diethyl ether was added to the solution from the dropping funnel under a nitrogen atmosphere, and the reaction was carried out under reflux <SSC> for 4 hours. went. A diethyl ether solution of ethyl acetate was added dropwise from the dropping funnel to decompose excess Mueh ASH4, and dilute sulfuric acid was further added to perform hydrolysis. Produced polymer 110
It was washed 5 times with 0 JllJ of methanol and dried under reduced pressure.

When the obtained polymer was analyzed by ftIR, the absorption spectrum of t723cyyl due to the carbonyl group completely disappeared, and a new broad absorption based on the absorption of the hydroxyl group was observed near 3300c1rr1.

Therefore, it was confirmed that the obtained polymer was a terminal-modified propylene polymer with a hydroxyl group represented by the following formula.

CH.

+CH2-CjH-i CH2-OH (average value of n is approximately 100) Example 3 Reaction with trimethylchlorosilane A terminal hydroxylated propylene polymer was synthesized in the same manner as in Example 2. In the system where the polymer 521n9 is present,
55 mmol of trimethylchlorosilane and 259 mmol of pyridine
The reaction was carried out at 25° C. for 4 hours. The resulting polymer T-100 traces were washed five times with methanol and further dried under reduced pressure.

When the obtained polymer k,'HNMR analysis was performed, δ=
At 0.08 ppa+, a signal due to the 3-group nofluoroton was measured #M, and a signal δ = 0.7 to 1.
From the intensity ratio with 7 ppm, 1n=4,700 was determined. This value is Mn = 4,4 measured by CPC of terminally aldehyde-terminated propylene summer coalescence in Example 2.
It matches well with 00.

As a result, it was proved that the filtration hydrogenation reaction in Example 2 and the subsequent trimethylsilylation reaction of this example were carried out quantitatively.

Therefore, the polymer obtained above was confirmed to be a propylene polymer having the following formula.

CH.

(Average value of n is approximately 100) Example 4 A polymer was obtained in the same manner as in Example 1 except that ethylene oxide was used in place of propylene oxide.

The resulting polymer had a GPC Un of 2.100, Mw/Mnril, and S of 6. As a result of this polyff-0IR analysis, a broad peak based on hydroxyl groups was observed near 5,500 tn-'. From Example 1 and the above results, it is presumed that a polymer having the following structural formula was produced.

CH3 100H2-CH+7-0H2-OH2-OH (average value of n is about 50) Example 5 Propylene living in the same manner as in Example 1 except that 830 mmol of propylene was used and the submergence time was t-3 hours. Polymerization was carried out and further treatment was carried out in the same manner as in Example 1 to obtain a polymer.

The Mn of the obtained polymer was 15,000, My/Mn
was 1.1. As a result of IR analysis, 3500 (B-'
A broad peak based on hydroxyl groups was observed nearby. From these results, 411! is the same as in Example 1! It became clear that polymer +1) and polymer (2) of the formula (however, the average value of n in the structural formula was about 560) were obtained.

[Brief explanation of the drawing]

Figure 1 is an NMR chart of the uninvented polymer; Figure 2 is an NMR chart of the uninvented polymer;
The figure is a partially enlarged view of figure 15g1.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R is an alkylene group having 1 to 8 carbon atoms which may be branched, R^1 is a hydrogen atom, or ▲ Numerical formula, chemical formula, There are tables etc. ▼, n is about 20 to about 1
0,000, and R^2 to R^4 are the same or different alkyl groups having 1 to 8 carbon atoms. ] Terminal-modified propylene polymer.