JPS62292809A - Novel polymer - Google Patents

Abstract

PURPOSE:To obtain an aromatic vinyl compound polymer having hydroxyimino groups, by protecting the hydroxyimino group of a hydroxyimino group- containing aromatic vinyl compound with a specified protective group, subjecting this compound to anionic living polymerization and eliminating the protective groups from the obtained living polymer. CONSTITUTION:A novel polymer having repeating units of formula I (wherein R<1> is H or methyl and n is an integer >=2) can be obtained, for example, in the following way. A vinyl compound of formula II (wherein R is H or methyl) is contacted with a compound having a substituted silyl group of the formula: R<2>R<3>R<4>Si- (wherein R<2>, R<3> and R<4>, which may be the same or different, are each alkyl or aryl) and the obtained vinyl compound having a substituted silyl group is polymerized by using a specified anionic polymerization initiator (e.g., oligo-alpha-methylstyrene dipotassium salt) to obtain a living polymer. This polymer is contacted with a proton donor (e.g., hydrochloric acid) to remove the substituted silyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polymer of an aromatic vinyl compound having a hydroxyimino group.

[Conventional technology]

Conventionally, polymers with hydroxyimino groups in their side chains have been used in many applications such as chelate resins that capture heavy metal ions in water, and the majority of them have been produced by introducing human miximino groups into crosslinked polymeric substances through polymeric reactions. It had been.

For this reason, there is no known example of producing a polymer in which an aromatic vinyl compound having a hydroxyimino group, that is, an aromatic aldehyde oxime vinyl compound, is polymerized using a radical polymerization initiator.

Furthermore, since the above-mentioned vinyl compounds have reactive active hydrogen and C=N- bonds in their molecules, anionic living polymers of the vinyl compounds have not yet been obtained.

The present inventors first protected the reactive groups of an aromatic vinyl compound having reactive groups such as hydroxyl, amino, formyl, and carboxyl groups in the molecule with a "Jt" group, and then
It has been discovered that an anionic living polymer of an aromatic vinyl compound having a protected reactive group can be obtained by the action of an anionic polymerization initiator [JP-A-5
Publication No. 9-53509; Polymer Proceedings, Volume 34, No. 2,
Page 195 (1985): Polymer Proceedings, Volume 34, 6
No. 1445 (1985)).

[Problem that the invention seeks to solve]

The object of the present invention is to synthesize a polymer of an aromatic vinyl compound having a hydroxyimino group in the molecule as a repeating unit.

[Means for solving problems]

(Summary of the Invention) As a result of extensive research, the present inventors have determined that the active hydrogen in the hydroxyimino group of an aromatic vinyl compound having a hydroxyimino group is preliminarily replaced with a trialkylsilyl group, triarylsilyl group, etc. (hereinafter referred to as , referred to as a substituted silyl group), oligo-α-methylstyrene dipotassium salt, 1
．． 1.4.4-Tetraphenylbutane dipotassium salt, 3
- When a specific anionic polymerization initiator such as methyl-1,1,3-triphenylbutane potassium salt is applied, the active hydrogen is protected against the anionic polymerization active species;
Furthermore, it becomes possible to suppress undesirable side reactions between the anionic polymerization active species and the reactive ':;c=N-bond, and it is possible to suppress the undesirable side reactions between the anionic polymerization active species and the reactive ':; The present invention was completed based on the discovery that a polymer was obtained, and then the substituted silyl group was removed by the action of a proton donor, yielding a polymer of an aromatic vinyl compound having a hydroxyimino group.

That is, the gist of the present invention is a novel polymer having a repeating unit of the general formula (wherein R' is a hydrogen atom or a methyl group, and n is an integer of 2 or more).

(Production method of novel polymer) An example of the production method of the novel polymer (1) according to the present invention is a method using anionic polymerization.

That is, the novel polymer of the present invention (RI) is a vinyl compound (II) represented by the general formula (in the formula, R1 represents a hydrogen atom or a methyl group) with the formula R"R"R' S
i - (where RξR1 and R' are the same or different alkyl groups or aryl groups), and the resulting vinyl compound is brought into contact with a substituted silyl group-containing compound represented by a specific anionic polymerization initiator. The substituted silyl group can be produced by polymerizing the substituted product to form a pasting polymer, and then contacting the substituted silyl group with a proton donor to remove the substituted silyl group.

Specifically, the vinyl compound (II) is 4-vinylbenzaldehyde oxime and 4-(1-methylvinyl).
Both benzaldehyde oxides and 6C1 can be used to produce the above polymer (1) in the same manner.

The substituted silyl group-containing compound used to protect the reactive group of the vinyl compound (n) is a compound containing a trialkylsilyl group, an alkyl/aryl mixed trisubstituted silyl group, or a triarylsilyl group. For example, the compound has the general formula (R"R"R' Si
) mX (wherein R8, R1 and R4 are the same or different alkyl groups or aryl groups, X represents a halogen atom or an NH group, m is 1 when X is a halogen atom, and in the case of an NH group is 2.), and a specific example thereof is ((CHs)ssi:IzNHl((CzH
i) sS i ) tNHl((ilio-CsHy
)ssi)zNH, (CH3)sSiCl, (Cx
Hs)ssict, t-C4HtCHs)*5iCt
, 1so-CsHt(CHJtSiCt, CHs(C
tHshSict, (n-C4HJsSi(J.

((CsHJ熁l)鵞さ■(、(CaHi(CHD鵞S
i:l! NH1(CaHi)*CaHsSiC! .

CH3CH3CHi etc. can be listed. These compounds can also be used in combination of two or more, vinyl compound (II)
The contact between the compound and the substituted silyl group-containing compound is usually carried out at room temperature or under heating for 0.5 to 50 hours. The contact may be carried out in a solvent or in an atmosphere of an inert gas such as nitrogen gas. Suitable solvents include N,N-dimethylformamide, tetrahydrofuran (hereinafter referred to as T)I
It is abbreviated as F'. ), N-methylpyrrolidone, sulforane, dimethylsulfoxide and the like.

The contact ratio between the two is such that the t-substituted silyl group-containing compound is 0.5 times or more mole or more, preferably 1 mole or more, relative to the vinyl compound (+1).
~10 times the molar amount.

In this way, the active hydrogen in the reactive group of the vinyl compound (1) is substituted with the substituted silyl group to form the vinyl compound (1).
The nuclear substituted product is then subjected to anionic polymerization in the presence of a specific anionic polymerization initiator to obtain a clinging polymer of the substituted product.

The specific anionic polymerization initiator used in the anionic polymerization of the substituted product is specifically oligo-α-methylstyrene dipotassium salt, 1,1,4.4-tetraphenylbutane dipotassium salt, 3-methyl-1 , 1°3-triphenylbutane potassium salt and the like.

The anionic polymerization is carried out at -100°C to room temperature, preferably at a low temperature of -30°C or lower, particularly preferably at -50°C to room temperature.
It is carried out at a low temperature of -100°C for 0.1 to 24 hours. Although the polymerization reaction may be carried out without a solvent, it is preferably carried out in the presence of a solvent. Suitable solvents include THF, hexane, toluene, cyclohexane, pentane, benzene and the like, and two or more of these may be used in combination.

In addition, the 1-polymerization system must be maintained in an inert gas atmosphere free of moisture and oxygen that would interfere with the polymerization reaction, or under reduced pressure, particularly preferably under high vacuum.

The molecular weight of the living polymer can be controlled by changing the ratio of the substituent/anionic polymerization initiator,
By increasing the ratio, the molecular weight can be increased. The resulting polyurethane polymer is usually about SOO
~About soo, ooo.

It has a number average molecular weight and is stable at relatively low temperatures.

Examples of the proton donor used to remove the substituted silyl group, which is a protective group, from the living polymer include methanol, ethanol, phenol, hydrochloric acid, sulfuric acid, and tetra-n-butylammonium fluoride.

The contact between the living poly i- and the proton donor is carried out in a solvent,
This is usually carried out at room temperature for 0.1 to 24 hours.

As a suitable solvent, the above-mentioned anionic polymerization solvent can be used, and THF is preferable. The contact ratio between the two is such that the proton donor is at least 0.5 times the mole of the substituted silyl group present in the living polymer, preferably 0.5 to 1.
It is twice the mole.

The novel polymer (1) thus obtained usually has a molecular weight of about SOO to
about soo, ooo, preferably about 2,000 to about 200
,000, particularly preferably about s, ooo to about 100.0
It has a number average molecular weight of 0.00 and an extremely narrow molecular weight distribution in which the ratio of weight average molecular weight/number average molecular weight is close to 1.

〔Effect of the invention〕

The novel polymer (1) of the present invention has one hydroxyimino group per repeating unit, compared to conventional hydroxyimino group-containing polymer compounds in which hydroxyimino groups are introduced into polymers of aromatic vinyl compounds. It is a linear polymer with a well-defined structure containing groups.

Furthermore, when the above polymer (1) is produced using an anionic polymerization method, the molecular weight can be easily controlled, so the obtained polymer has the characteristics of having an arbitrary molecular weight and a narrow molecular weight distribution. have First, anionic polymerization is carried out almost quantitatively, and therefore the polymer can be obtained in high yield.

Polymer (1) Fi according to the present invention can be used as a functional polymer that captures heavy metal ions due to the chelate-forming ability of the hydroxyimino group, and its reactive substituents include cyan group, amine group, formyl group, and carboxyl group. It is also useful as a raw material for the synthesis of highly desirable functional polymers converted into other polar groups such as.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

[Example 1] (Polymerization apparatus used for anionic polymerization) After freezing, the anionic polymerization initiator solution and 7mer solution used for anionic polymerization were degassed in a high vacuum line and sealed in an ampoule with a break cool.

Anionic polymerization is carried out using the equipment shown in the drawing, in which a flask connected to a high vacuum line is connected to the above ampoules containing multiple anionic polymerization initiator solutions and monomer solutions, and a branch pipe for taking out the waste anionic initiator solution after washing the inside of the system. using
It was done in the following way.

First, flask 1 was kept at 10-5 mmHg K for 5 hours to degas it, and the vacuum line 6 was sealed at point A. Then, the seal of ampoule 2 containing one anionic polymerization initiator solution was broken, and flask 1 was removed. The inside of the system containing the liquid was thoroughly washed and led to a branch pipe 5, which was then sealed off at point B. Next, the flask 1 was cooled to -78°C, the seal of the ampoule 3 containing the Sonoji anionic polymerization initiator solution cooled to -78°C was broken, the anionic polymerization initiator was introduced into the flask IK, and then The monomer cooled to -78°C was similarly introduced into flask 1 from ampoule 4 and reacted for 10 minutes. The purified polymer was subjected to post-treatment and then subjected to characterization.

(o-(t-7'Tyldimethyl)-4-vinylbenzaldehyde oxime (abbreviated as VBO-tBuSi).

) Synthesis and identification of 4-vinylbenzaldehyde oxime (CH2=2.1
*38% by weight of N, N
- t-Butylchlorodimethylsilane ((CHs)sC(CHs)zSiCt) in dimethylformamide solution at 0°C.
) in N,N-dimethylformamide was added, and the mixture was heated at 0°C for 1 hour under a nitrogen gas atmosphere and at 25°C for 12 hours.
Stirring was performed for hours. Then, add the reaction mixture to 5% by weight sodium hydroxide solution, extract the product with dichloromethane, and distill under reduced pressure! DO-(t-butyldimethyl)-4-vinylbenzaldehyde oxime (V B
O-tBusi) was obtained in 84% yield, and further purified by vacuum distillation in the presence of Grignard reagent (CaHsCHxMgCL) to obtain VBO-tBusi. This VBO-tBuSi was 94~b.
, in CDCtI (TMS standard), and the following chemical shift values were determined.

0.23 ppm (s; 6H, 0-8t-CH
5), 0.99 ppm (S: 9H, Si-C-C
H3'), 5.25-5.73 ppm (2d; 2
H, J=+11 Hz, 18H; CHt-),
6.73ppm (2d; IH, CH=), 7A 9-7
-70 plum (m; 4H, Aromati
c).

8.18 ppm (s:IH, -CH=N-) From this chemical shift value, it was confirmed that VBO-tBusi has the following structure.

(Synthesis and Identification of Living Polymer of VBO-tBusi) VBO-tBusi was polymerized in THF at -78°C for 10 minutes using various anionic polymerization initiators shown in Table 1. In both cases, the color exhibited a slightly blackish red color characteristic of the polymerized exfoliating anion.

Poly(0-(t-butyldimethylsilyl)-4-vinylbenzaldehyde oxime) (PVBO -tBuS
i) was obtained quantitatively.

The results of 'HNMR analysis and IR analysis of PVBO-tBusi are shown below.

'HNMR: 0.21 ppm (s: 6H, 0-
8t-CH3), 1.00ppm (s; 9H, St
-C-CHs), 0.50 to 2.00 ppm (b
road: 2H, -CHz-CH-), 0.50~
2.00ppm(broad:ll(,C'HtC
H), 6.10-7.50ppm (broad:
4H, Aromatic), 8.05 ppm (s
;IH, -CH=N-) IR: 1613 and 1513cru (heyzene ring endoskeletal vibration), 1393 and 1364 cm,' (-C
(CHl)s), 1254 and 833 cm-'(S
i-C), 1660 cm-' (-CH-N-) From these analysis results, it was confirmed that PVBO-tBusi has the following structure.

(In the structural formula, n represents an integer of 2 or more) PVBO-t
Busi is THF, methyl ethyl ketone, benzene,
It was soluble in toluene, ethyl acetate, diethyl ether, chloroform, acetone, dioxane, and pyridine, and insoluble in hexane, N,N-dimethylformamide, dimethyl sulfoxide, ethanol, methanol, and water.

The intrinsic viscosity measured at 40°C after dissolving PVBO-tBusi in THF, and the intrinsic viscosity measured at 40°C using THF as a solvent, ft G P C (Gel Permiatio
The number average molecular weight was determined by the general purpose calibration curve method from the outflow curve of
Shown in the table. It can be seen that the measured value of the number average molecular weight of PVBO-tBuSi is in good agreement with the number average molecular weight calculated based on the molar ratio of VBOtBusi/anionic polymerization initiator.

Performed GPC measurement on PVBO-tBusi K,
The weight average molecular weight/number average molecular weight O value determined from the outflow curve was close to 1, confirming that the polymer had an extremely narrow molecular weight distribution.

From these analysis results, the nine polymers obtained by anionic polymerization of VBO-tBusi are:
It was proven that it is a living polymer with i repeating units.

PVBO-tBusi'k 1.0 with protecting group
% # /liter'D (CHs(CHx)s)4N
By treating with a THF solution of F (tetra-n-butylammonium 7yide) at room temperature for 24 hours)
, the protective group t-butyldimethylsilyl group is removed,
Poly(4-vinylbenzaldehyde oxime) (PVBO) is soluble in THF, acetone, dioxane, pyridine, ethanol, methanol, hexane, benzene, ethyl acetate, chloroform, N,N-dimethylformamide, dimethyl sulfoxide, and insoluble in water. I hope you get it. PVB
As a result of HNMR analysis and IR analysis of O, no characteristic absorption based on t-butyldimethylsilyl group was observed, and PVB
It was confirmed that O has the following structure. (In the structural formula,
n represents an integer of 2 or more. ) From these analysis results, the polymer obtained by anionically polymerizing VBO-tBuSi and removing the t-butyldimethylsilyl group, which is a protective group, is a polymer with repeating units of VBO. Proven.

(Margin below) Table 1 Explanation of anionic polymerization initiator abbreviations.

(α-M+eSt)4Kt: Oligo-α-methylstyrene dipotassium salt (D, Ph, E) K: 3-methyl-1,1,3-)liphenylbutane potassium salt (D, Ph, E) sK*: 1,1,4,4-tetraphenylbutane dipotassium salt [Example 2] (Synthesis and identification of 0-(iJ methylsilyl)-4-vinylbenzaldehyde oxime (VBO-TMS)) Synthesis and identification of 4-vinylbenzaldehyde oxime (VBO) 80
VBOK in wt% N,N-dimethylformamide solution
On the other hand, equimorno [(CH3)3Si]! Add NH (hexamethyldisilazane) and heat at 25°C under nitrogen gas atmosphere for 12 hours.
Stirring was performed for hours. The product is then distilled under reduced pressure to 0
-()Limethylsilyl)-4-vinylbenzaldehyde oxime (VBO-TMS) obtained in a yield of 86% and further purified by vacuum distillation in the presence of Grignard reagent CCaH6CHxMg CL).
Got nine. This VBO-TMS was 82~b o V B OT M S f: 'HNMR (
200MHz.

CDCJS, TMS standard) was used to determine the following chemical shift values.

0.29 ppm (s; 9H, 5i-CHs)
, 5.29-5.79ppm (2d:2H, J-11H
zl 17az, CHtz), 6.70Ppm (2d
: IH,CH=), 7.24-7.58ppm (
m: 4H.

Aromatic), 8.17 ppm (s: IH
, -CH=N-).

From this chemical shift value, it was confirmed that VBO-TMS has the following structure.

(In the structural formula, n represents an integer of 2 or more.) HI (Synthesis and Identification of VBO-TMS Pasting Polymer) Anionic polymerization was performed using the same polymerization apparatus and polymerization operation as in Example 1). 1.1.4 as an anionic polymerization initiator
．． Using 0.230 mmol of 4-tetraphenylbutane dipotassium salt, 4.05 mmol of VBO-TMS was
Polymerization was carried out in I'HF at -78°C for 5 minutes. It exhibited a slightly blackish red color that is characteristic of polymerized anions.

By adding a few drops of methanol to this living polymer and then treating it with a small amount of 2N hydrochloric acid at room temperature, the trimethylsilyl protecting group is removed and poly(4-vinylbenzaldehyde oxime) (PVBO) is quantitatively released. obtained.

As a result of 'HNMR analysis of PVBO, no signal derived from the proton of the trimethylsilyl group was observed, and it was confirmed from the proton ratio of each signal that PVBO had the following structure. Also, the IR spectrum of PVBO is 31
00-3500cm-'(-OH), 1612 and 15
18 cm-' (exhibited benzene absorption and supported the following structure. (In the structural formula, n represents an integer of 2 or more.) The obtained PVBO was diacetylated with acetic anhydride in a pyridine solvent, and then After purification by precipitation method, drying is performed,
Obtain acetylated PVBO. IH acetylated PVBO
) JMR analysis and PVBO from the proton ratio of each signal.
was confirmed to be quantitatively acetylated. The number average molecular weight was determined by the general-purpose calibration curve method from the intrinsic viscosity measured at 40°C after dissolving this acetylated PVBO in THF and the GPC runoff curve measured at <40°C using THF as a solvent. The measured number average molecular weight of acetylated PVBO is 6,700, which is in good agreement with the calculated number average molecular weight of 7.200 assuming that all hydroxyimino groups in PVBO are acetylated.

GPC measurement was performed on the acetylated PVBOtC, and the value of weight average molecular weight/number average molecular weight determined from the outflow curve was 1.16, confirming that the polymer had an extremely narrow molecular weight distribution.

These analysis results demonstrated that the polymer obtained by anionically polymerizing VBO-TMS and then removing the trimethylsilyl protecting group is a polymer having repeating units of VBO.

[Brief explanation of drawings]

FIG. 1 schematically shows an apparatus for carrying out anionic polymerization in the present invention. l... flask, 2,3... ampoule filled with anionic polymerization initiator solution, 4... ampoule filled with monomer solution,
5... Branch pipe, 6... Vacuum line, 7... Cock,
8°°° magnet. Patent applicant Mishima Paper Co., Ltd. Representative Motoyuki Miyoshi Figure 1

Claims (1)

[Claims] A new polymer having a repeating unit of the general formula ▲ Numerical formula, chemical formula, table, etc. .