JPS6386703A - Production of polymer with oxazoline ring at one end - Google Patents

Abstract

PURPOSE:To directly and readily obtain in high purity the titled polymer useful for production of functional polymers, by polymerization of a vinyl monomer carrying -CO or -CN group using a specific oxazoline as the initiator. CONSTITUTION:The objective polymer can be obtained by polymerization is the presence of a co-catalyst selected from polymerization initiators, fluorine compounds [e.g., tris(dimethylamino)sulfonium difluorotrimethyl silicate], N3<->- contg. compounds, CN<->-contg. compounds, Lewis acids (e.g., ZnCl2) and organometallic compounds (e.g., butyllithium), of a vinyl monomer having carbonyl or cyano group (e.g., methyl methacrylate, acrylonitrile) using, as the initiator, novel 2-oxazolines carrying trimethylsilyl group of formula I or II.

Description

Detailed Description of the Invention A) Purpose of the Invention [Field of Industrial Application] The present invention relates to a method for producing a polymer having an oxazoline ring (hereinafter also referred to as the polymer of the present invention), and Functional graft polymers, block polymers, etc. derived from
It is extremely useful as a raw material or intermediate for polymer molding materials such as adhesives, adhesives, sealants, dispersants, rubbers, and plastics, surface modifiers, and fine chemicals such as pharmaceuticals and agricultural chemicals.

[Conventional technology]

The oxazoline ring can be easily converted into carboxylic acid by hydrolysis, and can be applied in many fields, such as by ring-opening polymerization using cationic catalysts to produce poly(N-acylethyleneimine). It is a reactive atomic group that can be expected to be highly valuable for creating functional polymers.

Conventionally, attempts to synthesize functional polymers by introducing an oxazoline ring into a polymer have been made by anionically polymerizing a monomer having an oxazoline ring at the para position of styrene, and then hydrolyzing it to form a poly(4 -vinylbenzoic acid) (A, Hirao
et al, Polymer Pre-print
ts Japan, 34 (6), 1445 (
1985) ).

Furthermore, when synthesizing poly(N-acylethyleneimine) by ring-opening polymerization of 2-oxazolines, an initiator having a vinyl group such as vinylbenzyl bromide is used to synthesize poly(N-acylethyleneimine) having a vinyl group at the end ( It has also been reported that poly[styrene-g-(N-acylethyleneimine)] can be obtained by synthesizing N-acylethyleneimine (macromonomer synthesis) and radical copolymerizing it with styrene (S, Kobaysashi et a
l, Polymer Pre-prints Jap
an, Gong, 1353 (1985)).

[Problem that the invention seeks to solve]

In these conventional methods, it is possible to introduce an oxapurine ring into a pendant of the polymer backbone, or to introduce poly(N-acylethyleneimine) into a graft polymer technique, but it is possible to introduce an oxazoline ring at one end, Introducing oxazoline rings into polar polymers such as methyl methacrylate has been very difficult due to side reactions caused by the highly reactive oxazoline rings.

α,β-unsaturated unsaturated nylbonyl compounds such as methyl methacrylate, ketene silyl acetals such as methoxy-1-trimethylsiloxy-2-methyl-1-propene are used as polymerization initiators, It is known from the Web
This was revealed in the research of ster et al.
-13603 Publication, A CB Polymer
Webster et al. named this new polymerization method the group transfer method.

This method is explained as follows. That is, strictly speaking, α, β-, β-ester of ketenesilylacecur,
It is defined as a polymerization reaction that proceeds by repeated Michael additions to nitriles or carboxamides. A polymerization initiator having an active trimethylsilyl group (1-methoxy-1-trimethylsiloxy-2-methyl-1-propene (such as compound (1) below) and a cocatalyst (H
F-2, etc.) using methyl methacrylate (hereinafter referred to as MM
A typical example of polymerizing an α,β-unsaturated carbonyl hexamer such as A) is shown in the following reaction formula.

Catalyst (HF″2) 0-5 L (CH:l) MMA HF-.

Living polymer (3) In other words, the polymerization initiator performs a Michael addition to the MMA monomer, and then the trimethylsilyl group moves intramolecularly to the MMA end (formula 2) above, and polymerization progresses sequentially by repeating this addition and transfer reaction again. .

At this time, throughout the polymerization, the growing end always proceeds while taking the same ketene silyl acecool end group structure as the polymerization initiator (1) (formulas (2) and (3) above), and the living polymer (3).
generate.

The molecular weight of the resulting slipping polymer can be controlled by the ratio of the polymerization initiator and monomer concentration used for polymerization.
Furthermore, a nearly monodisperse polymer can be obtained.

In addition to the polymerization initiators shown in (1) above, Webster et al. have also synthesized living polymers using polymerization initiators such as:

However, all of these polymerization initiators used by Webster et al. have the general formula ketenesilylacecur, and have a substituent (R.

Since R, R) does not have a structure having an oxazoline ring, it is difficult to directly produce a polymer having an oxazoline ring at one end when polymerizing using these polymerization initiators. there were.

g) Structure of the invention [Means for solving the problem] The present inventors polymerized α,β-unsaturated unsaturated nibonyl monomers such as acrylates or methacrylates, and directly produced monomers containing cyano groups. As a result of intensive research into a method for producing a polymer with an oxazoline ring at one end, a new compound with a specific chemical structure was synthesized, and by using this as a polymerization initiator, it was possible to create an oxazoline ring at one end. The present invention was completed based on the discovery that it is possible to produce a polymer having the following properties.

That is, the present invention combines a vinyl monomer having a carbonyl group or a cyano group with a polymerization initiator and a fluorine compound, N
-3, a compound having CN-, a Lewis acid, and an organometallic compound.
This is a method for producing a polymer having an oxazoline ring at one end, which is characterized by using a 2-oxazoline having a trimethylsilyl group represented by:

-CH2 (hereinafter abbreviated as TMSi-2Me-2-Oxz)CH
Co-CH2 (hereinafter abbreviated as TMSi-2-Et-2-Oxz) [
Vinyl monomer having carbonyl group or cyano group] The monomer used in the present invention is a vinyl monomer having a carbonyl group or cyano group.

Examples of the vinyl monomer having a carbonyl group include acrylate or methacrylate (hereinafter referred to as (meth)acrylate), ethyl vinyl ketone, and the like. Among these, 4t (R is H, CH3, R is C9-C□furkyl, C
Preferred are (meth)acrylates of the formula =~% cycloalkyl, phenyl, aralkyl and any of the above groups having one or more functional groups which are non-reactive during the polymerization conditions.

Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate.
Acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 1°sononyl (
meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2
-Acetoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, allyl (meth)acrylate, glycidyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethyl Examples include, but are not limited to, carpitol (meth)acrylate.

More preferred monomers include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.
acrylate, 2-acetoxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate. A particularly preferred monomer is methyl methacrylate.

Examples of the vinyl monomer having a cyano group include acrylonitrile and ethyl-2-cyanoacrylate.

[Co-catalyst]

The cocatalysts used in the present invention are fluorine compounds, compounds with N-3, compounds with CN-, Lewis acids or organometallic compounds, which are known compounds or by known methods. It is manufactured by.

Fluorine compounds useful in the method of the invention include fluorideones ( F-) source is preferred, and a particularly preferred cocatalyst is tris(dimethylamino)sulfonium difluorotrimethylsilicate (hereinafter abbreviated as TASF2 SiMe) which is bifluoride (F″2-). Tris(dimethylamino)sulfonium bifluoride Ride can be easily produced by reacting TASF2SiMe with water or methanol.

Examples of the Lewis acid include ZnCl2 and the like.

In addition, examples of organometallic compounds include butyllithium, trityllithium, lithium diisopropylamide, lithium trimethylsilate, lithium triphenylsilate, sodium trimethylsilate, sodium triphenylsilate, trityl sodium, and sodium tritylsilate.
α-methylstyrene tetramer dianion, potassium-
Preferred are organometallic compounds whose counter ion is an alkali metal, such as α-methylstyrene dimer dianion, cumyl potassium, potassium tert-butoxide, and cumyl cesium, and particularly preferred are butyl lithium,
Potassium-terL-butoxide.

[Polymerization initiator]

The polymerization initiator used in the present invention is a 2-oxazoline having a trimethylsilyl group, and specifically, TMS
i2 M e 'l -□ z z or TMS
1-2-Et-2-Oxz. Kot'L is a new compound, and the applicant has filed a separate application for this new compound (patent application (1) filed on September 30, 1985).
).

TMS i-2-Me-2-Oxz or TMSi
An example of the synthesis of 2-Et-2-Oxz is as shown in Example 6 below, and the synthesis scheme is as follows.

(CNco)35i (X=H,CNco) That is, commercially available 2-methyl-2-oxazoline or 2-
Using ethyl-2-oxazoline as a starting material, α
- After the hydrogen is anionized, it is reacted with trimethylchlorosilane (hereinafter abbreviated as TMC8) to obtain a 2-oxazoline having a trimethylsilyl group.

Incidentally, reactions similar to the above synthesis scheme have already been reported as follows.

C, Ainsworth et al. J, Organometal
lic Chemistry 46 In addition, the polymerization initiator of the present invention TMSi-2-Me2-Oxz or TMS 1
The method for producing -2-Et-2-OX2 is not limited to this.

[Method for producing a polymer having an oxazoline ring at one end]

The method for producing a polymer having an oxazoline ring at one end of the present invention includes a fluorine compound, a compound having N''3, a CN
When using a cocatalyst selected from a compound having - or a Lewis acid, the group transfer polymerization method is used in principle, and when an organometallic compound is used as a cocatalyst, the anionic polymerization method is used.

That is, for example, when a fluorine compound is used as a cocatalyst and a monomer is methyl methacrylate (hereinafter abbreviated as MMA), the polymerization scheme of the present invention is as shown below.

C) (2-OH 111 Tetrahydrofuran CH2(, -C-R \Z l nMMA, HF2N
5i (CN ko) ko cii2-o Il CH2C-C-R'' CIl ko C
11C02C)1R''; II-TMSi-2-Me-2-Oxz
CH3-TMSI-2-ECZ-Oxz (living polymer) Ct12-0 1-1 methanol 1 11 Cl12 C-C-RC1l:1 1paco2cu (macromonomer) For example, when an organic gold mud compound is used as a cocatalyst As an example, the scheme of the present invention when butyllithium is used as a cocatalyst and MMA is used as a monomer is as shown below.

CIl2-O11 111n-Butyllithium C112C-C-R''- \ / 1 -78℃ Tetrahydrofuran N
5i (CIlco).

C112-OLI C112-OS i (CIl:l))C
112C-C-R” CI (1C11゜C02
CII OL+R': H=TMSi 2-Me-2-OxzCH
:l =TMS 1-2-Et-2-Oxz (living polymer) CH2-OSi (CH co)comethanol 1 11 1 CH2C-C-RCH co2crico (macromonomer) Thus, one end is reactive This is a production method that is industrially very advantageous because the polymer (5) or (8) having a high oxazoline ring can be directly obtained.

That is, the fundamental difference between the method of the present invention using the group transfer polymerization method and the method of Webster et al. This is because it was used as a polymerization initiator. This new polymerization initiator has made it possible to directly produce a polymer having an oxazoline ring at one end.

In the present invention, the number average molecular weight of the polymer of the present invention is preferably 1,000 to 400,000. The number average molecular weight is a polystyrene equivalent molecular weight determined by gel permeation chromatography, and the measurement conditions are as follows.

Apparatus: High performance liquid chromatography (for example, Toyo Soda Kogyo Co., Ltd. product name 1 (L C-802UR)) Column: Polystyrene gel (for example, Toyo Soda Kogyo Co., Ltd. product name G 40001 (8 and G3000) I8) Elution solvent: Tetrahydrofuran Outflow rate: 1. On+l/a+in column temperature:
40° C. Detector: RI detector In the method for producing the polymer of the present invention, it is preferable to use a solvent in order to control the generated polymerization heat, but it is not essential. Any solvent can be used as long as it is non-reactive with the monomer, polymerization initiator, and cocatalyst and has sufficient solubility, such as ethyl acetate, toluene, xylene, benzene, and tetrahydrofuran (T) IF. ), acetonitrile, N,N-dimethylformamide, etc., and THF is most preferred.

The monomers used in the present invention are generally liquid and are preferably used at a concentration of at least 1% by weight.

The amount of the polymerization initiator used is determined by the target molecular weight of the polymer of the present invention and the initiation efficiency described below, but it is usually preferable that the molar ratio of the monomer 71 initiator is in the range of 1 to 100. .

The amount of cocatalyst used is preferably in proportion to the polymerization initiator, and the molar ratio of polymerization initiator/cocatalyst is 1 to 500.
is preferable, and 2 to 20 are more preferable.

The polymerization temperature is preferably -100°C to 100°C, more preferably 0°C to 50°C, and even more preferably 0°C to room temperature.

The polymer of the present invention can be obtained by contacting the polymer obtained as described above with an active hydrogen source, such as water or alcohol.

[Application of polymer with oxazoline ring at one end]

Since the polymer of the present invention is synthesized using a polymerization initiator having an oxazoline ring, the purity of the polymer having an oxazoline ring at one end is extremely high. (for example, 2-methyl-2-oxazoline), a comb-shaped graft polymer with poly(meth)acrylates in the branch segments and poly(N-acylethylenesimine) in the main chain can be easily produced. do. At this time, the type of comonomer,
By controlling the charging ratio of the polymer of the present invention/comonomer, etc., it is possible to produce a desired mechanical lateral graft polymer with a clear structure.

In addition to the above-mentioned uses as ring-opening polymerizable macromonomers, there are also uses that utilize the reactivity of the oxazoline ring, such as reactions with carboxyl groups, acid anhydrides, phenolic hydroxyl groups, amino groups, mercapto groups, epoxy groups, etc. It can be used as a functional polymer raw material or a modifier. Furthermore, after converting the oxazoline ring into a carboxyl group by treating it with an acid or an alkali, this terminal carboxyl group polymer can be used for similar purposes.

[Reference examples, examples and application examples]

The present invention will be explained in more detail below with reference examples, examples, and application examples. Note that parts are by weight.

Reference Example 1 (Synthesis of TMS i-2-Me-2-Oxz) Stirrer,
After the glass flask-3 equipped with a temperature needle, dropping funnel, and Dimroth condenser was sufficiently replaced with nitrogen, 268 gr of 8% LDA/THF solution was put into the flask under a nitrogen atmosphere.
2-Methyl-2-oxazoline 17. while cooling from the outside with a dry ice-methanol bath. After Ogr was added dropwise over 5 minutes, the mixture was further stirred and reacted for 30 minutes while maintaining the temperature below -20°C. Then, at the same temperature, excess T
MC554, 3 gr was added dropwise over 5 minutes.

While stirring, slowly return the temperature of the liquid to room temperature, and let it cool for 30 minutes at room temperature.
After a few minutes had elapsed, the reaction solution was filtered and the filtrate was concentrated using a rotary evaporator. The residue was washed with anhydrous ethyl ether and filtered, and the desired product was extracted into anhydrous ethyl ether.Then, the anhydrous ethyl ether was removed using a rotary evaporator, and the remaining oily liquid was distilled. As the main fraction, 13.9 gr of a fraction having a temperature of 140° C. to 145° C. in air was obtained. The yield was 44.25%.

In the IR spectrum, as shown in Figure 1, the absorption peak due to 5i-C is strong near 850 crs-', and the absorption peak derived from the C-N bond (substituted imine) is 1.
Since it appears strongly in the vicinity of 600-1650 c++-', it is fully confirmed that it has a TMS i-2-Me-2-Oxz structure.

The I H-N MR spectrum is 5 as shown in Figure 2.
The peak based on i-(CH co)3 is around 0.2δ, and the peak based on 5
The peak based on i-CH2O is around 1.8δ, -0-
Based on CII2-CH2-N < peak is 3.8-4.0
It is seen near δ.

As shown in Figure 3, the C-NMR spectrum also shows that the peak is around -6°2δ based on 5i-(C1lco)3, and the peak power based on Si-CH2-Ck is 13.8δ.
Nearby, there is also a peak based on -〇-CH2- at 67.2
to δ, =N−C)12-1. The peak based on m is 54.6
6 and a peak based on -0-C=N- can be seen at 167.86, respectively.

The elemental analysis value is C: 53.34% (calculated value 53.39%
), H: 9.69% (calculated value 9.61%).

Reference Example 2 (Synthesis of TMSi-2-Et-2-Oxz) The reaction was carried out in the same manner as in Reference Example 1 except that 2-ethyl-2-oxazoline was used instead of 2-methyl-2-oxazoline. After removing the ether, the oily liquid was distilled under reduced pressure to obtain a main fraction at 75°C/50 vsHg.The yield was 20.0%.

For the obtained TMS 1-2-Et-2-Oxz I
As a result of measuring the R spectrum, as shown in Figure 4, 5
The absorption peak due to t-C is around 850 cm-',
= Absorption peak derived from N bond is 1600-1650
It was confirmed that it appeared near cta-'.

The IH-NMR spectrum is as shown in Figure 5, with peaks based on 3i-(CH)co around 06 and -
The peak based on CH2-CH is around 1δ, and the peak based on -0-C
It was confirmed that a peak based on H2CH2-N- was present at around 3.5 to 0.5 Oδ.

'C-NMR spectrum is as shown in Figure 6,
The peak based on 5i-(CHco)co is at -2,86, -
The peak based on CH is 12.1δ, the peak based on CH2-3i is 23.3δ, the peak based on N-CH2- is 54.4δ, and the peak based on -CH2-0- is 67.
．． It was confirmed that a peak based on 06 and N=C-0- was present at 171.96.

Example 1 Polymerization initiator TMSi-2-Me-2-Oxzo, 133 parts (1,
56sv+ol), cocatalyst TASF2SiMe:)0
．． 02 parts (0,078 s+mol) and 9.70 parts (0,097 mol) of MMA purified in calcium hydride (Ca H2) were added and polymerized for 1 hour at room temperature. After adding methanol to stop the reaction, reprecipitation purification with n-hexane solution resulted in Mn = 18,700.
0. PolyMMA having an oxazoline ring at one end with Mw/Mn -2.50 was obtained in a yield of 96.2%. The starting efficiency was 3.3%. Incidentally, the initiation efficiency is determined by the following formula based on the theoretical average molecular weight determined by the following formula.

(Theoretical average molecular weight = (molecular weight of monomer) x (number of moles of monomer) / (number of moles of polymerization initiator) (initiation efficiency) (%) - (theoretical average molecular weight) / (synthesized polymer molecular weight X1
00 Also, when the properties of this polymer were examined by IH-NMR spectrum, the syndiotactic value was 59.
1%, heterotactic at 36.9%, and isotactic at 4.0%.

Examples 2-6 MMA monomer and polymerization initiator TMSi 2 Me-2
- The charging molar ratio with Oxz, reaction temperature and time are
Polymerization was carried out in the same manner as in Example 1, with the changes shown in the table. The results are shown in Table 1.

Example 7 Polymerization initiator TMSi-2-Et-2-Oxzo, 082 parts (0,
827m+mol) and cocatalyst TASF2 S 1M13
30.02 parts (0,083 nuiol) and Ca11
6.70 parts (0,067 mol) of MMA purified in
) was added and polymerized for 30 minutes at 0°C. After adding methanol to stop the reaction, reprecipitation purification with n-hexane solution resulted in "lower = 4° 21000, Mw/Mn-1
, 98 having an oxazoline ring at one end was obtained in a yield of 92.8%. The starting efficiency was 1.9%.

Example 8.9 Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 2 using a mixture of T)IF-acetonitrile (CH3CN) as the solvent. The results obtained are shown in Table 2.

Example 10 Polymerization initiator TMSI-2-Me-2-Ox under high vacuum system
zO, 266 parts (3.12 mmol) of anhydrous THF20
ml solution and cocatalyst n-butyllithium (n-BuLi)
TMS
After i-2-Me-2-Oxz-lithium, MMA
lo, 5 parts (0,105 n+ol) of anhydrous THF80
i1 was added, and the polymerization reaction was carried out at -78°C for 18 hours. After adding methanol to stop the reaction, poly-IJMMA having an oxazoline ring at one end of re-1,66 was obtained with a yield of 100% using an n-hexane solution. Starting efficiency is 44.
It was 1%.

Examples 11-13 MMAfl polymer and polymerization initiator TMSi-2-Me-2-
Polymerization was carried out in the same manner as in Example 10, except that the molar ratio of Oxzs cocatalyst n-BuLt, reaction temperature and time were changed as shown in Table 3. The results obtained are shown in Table 3.

Application Example 0.30 part of polyMMA (Mn=8580) having an oxazoline ring at one end, obtained in the same manner as in Example 1.
0,035 mmol), 2-methyl-2-oxazoline 1.00 part <11.8 mmol), polymerization initiator benzyl tosylate 0.80 part (0,3211II*ol)
was dissolved in 7 ml of nitrobenzene and heated at 80°C under nitrogen atmosphere.
Cationic ring-opening polymerization was carried out for 18.5 hours. By extracting and purifying with water and benzene, polyMMA and poly(N
- acylethyleneimine) homopolymer is separated, and the desired branch segment has polyMMA and the main chain is poly(N
- acylethyleneimine) graft copolymer 1.30
(100% yield).

As a result, in polyMMA having an oxazoline ring at the end, there is approximately one oxazoline ring at one end per molecule.
It can be seen that each individual has been introduced.

c) Effect of the invention According to the present invention, by using a vinyl monomer having a carbonyl group or a cyano group and using a specific oxazoline as a polymerization initiator, a polymer having an oxazoline ring at only one end can be produced. It can be easily produced directly with high purity.

In addition, since the polymer of the present invention has a highly reactive oxazoline ring at the end, it can be converted into a carboxy group by hydrolysis with an acid or base, or a highly functional graft copolymer can be synthesized by ring-opening polymerization. It is extremely effective for creating polymers with high industrial value.

[Brief explanation of the drawing]

Figures 1 and 2.3 show the TMS i obtained in Reference Example 1.
IR spectrum of -2-Me-2-Oxz, 'H-NM
R spectrum, 11C-NMR spectrum is shown, and the fourth
．． Figure 5.6 shows TMS 1-2 obtained in Reference Example 2.
IR spectrum of -Et-2-Oxz, I H-N M
R spectrum and 11C NMR spectrum are shown.

Claims (1)

[Scope of Claims] 1. A vinyl monomer having a carbonyl group or a cyano group is combined with a polymerization initiator and a fluorine compound, a compound having N^-^3, a compound having CN^-, a Lewis acid, and an organic metal. When polymerizing in the presence of a cocatalyst selected from the compounds, a 2-oxazoline having a trimethylsilyl group represented by the following formula (I) or (II) is used as a polymerization initiator. A method for producing a polymer having a ring. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II)