JP3015088B2 - Macromonomer - Google Patents

Description

The present invention relates to a polyvinyl ester macromonomer.

The polyvinyl ester-based macromonomer of the present invention can be used as a raw material for the synthesis of a graft polymer whose composition, structure, molecular weight, and the like are highly controlled.

The graft polymer obtained by using the macromonomer of the present invention has higher utility in various fields of application such as paints, adhesives and compatibilizers than the graft polymer obtained by the conventional method.

B. Prior Art Macromonomers have recently attracted attention as a raw material for the synthesis of highly controlled graft polymers, and an extremely large variety of macromonomers have been synthesized.

However, when looking at polyvinyl ester-based macromonomers, only a few examples have been reported. For example, a polyvinyl acetate macromonomer having a terminal olefin (see JP-A-63-95215). Abbreviations) and styrene-terminated polyvinyl acetate macromonomers (see J. Polymer Sci., PC, 25 , 175 (1987); hereafter abbreviated as literature (B)). In addition, the homopolymerizability and the copolymerizability with other monomers are low, and it is difficult to obtain a polymer having a high degree of polymerization. Further, since the polyvinyl acetate macromonomer disclosed in the document (B) has a cationic group in the linking group portion, there is a problem that its use range is greatly limited.

C. Problems to be Solved by the Invention The present invention aims to provide a polyvinyl ester-based macromonomer having excellent polymerizability and a short molecular weight distribution.

D. Means for Solving the Problems The present inventors have conducted intensive studies on the above problems and found that the general formula [However, R ^{1 is a} hydrogen atom or a methyl group (X): a linking group bonded to S on the R ² side shown below] (R ² represents an optionally branched alkylene group having 2 to 20 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 4 or less carbon atoms.) (PVES): containing a vinyl ester unit A monovalent polyvinyl ester polymer having a number average degree of polymerization of 3 or more (however,
Excluding those containing vinyl alcohol units). ] And have completed the present invention.

 Hereinafter, the present invention will be described in detail.

The polyvinyl ester-based macromonomer of the present invention is composed of a polymerizable double bond portion at one end, a polyvinyl ester-based polymer portion, and a portion connecting both, and is represented by the above general formula (I).

The polymerizable double bond portion at one end is acrylamide or methacrylamide, and the double bond is bonded to the polyvinyl ester-based polymer by a connecting group (X) composed of an amide group and an alkylene group and a sulfur atom. I have. This linking group (X) is (R ² represents an alkylene group which may 2-20 carbon atoms which may have a branched, R ³ represents. A hydrogen atom or an alkyl group having 4 or less carbon atoms), and combined with S in R ² side are doing. Specific examples of R ² include _{- (CH 2) 2 -,} - (CH 2) 3 -, - (CH 2) 6 -, - (C
H ₂ ) ₁₀ — and the like, and specific examples of R ³ include hydrogen, methyl, ethyl, propyl, and butyl.

The polyvinyl ester polymer (PVES) portion has a number average degree of polymerization of 3 or more, preferably 3 to 500, more preferably 5 to 300, and still more preferably the ratio of the weight average degree of polymerization to the number average degree of polymerization. Is a monovalent polyvinyl ester-based polymer having a distribution of the degree of polymerization and a shear of 3.0 or less,
A vinyl ester homopolymer or copolymer having a vinyl ester unit content of 30 mol% or more, preferably 50 mol% or more, is suitable. When the number average degree of polymerization of the polyvinyl ester type polymer portion exceeds 500, the polymerizability of the obtained polyvinyl ester type macromonomer decreases or the ratio of the weight average degree of polymerization and the number average degree of polymerization of the polyvinyl ester type polymer. (Less than,
Polymerization degree distribution or abbreviated as _w / _n ) is 3.
If it exceeds 0, there may be a problem that the properties of the graft polymer obtained from the polyvinyl ester-based macromonomer of the present invention are not sufficiently exhibited. Here, the polymerization degree distribution is based on GPC measurement (measurement conditions: tetrahydrofuran (hereinafter abbreviated as THF)) solvent, flow rate 1.0
ml / min, 25 ° C). Further, even when the content of the vinyl ester unit in the polyvinyl ester-based polymer is 30 mol%, the characteristics of the graft polymer obtained from the polyvinyl ester-based macromonomer of the present invention may not be sufficiently exhibited.

Examples of the vinyl ester (hereinafter sometimes abbreviated as VES) unit constituting the polyvinyl ester polymer portion of the present invention include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl valerate, and caprin. Units composed of vinyl acid, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl trifluoroacetate, vinyl trichloroacetate and the like are included. When the polyvinyl ester-based polymer is a copolymer, the comonomer (hereinafter sometimes abbreviated as CM1) is not particularly limited, and is selected from units that can be introduced by copolymerization. Such comonomer (CM
The following are examples of 1). That is, ethylene, propylene, 1-butene, olefins such as isobutene, acrylic acid or a salt thereof, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-acrylate
Acrylates such as -butyl, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methacrylic acid or a salt thereof, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacrylic Methacrylates such as i-propyl acrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N
-Dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid or a salt thereof,
Acrylamidopropyldimethylamine or a salt thereof and a quaternary salt thereof, acrylamide derivatives such as N-methylolacrylamide or a derivative thereof, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidopropanesulfonic acid or a salt thereof, methacryl Methacrylamide derivatives such as amidopropyldimethylamine or a salt thereof and a quaternary salt thereof, N-methylol methacrylamide or a derivative thereof,
Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether,
vinyl ethers such as n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether;
Nitriles such as acrylonitrile and methacrylonitrile; vinyl chlorides such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid or salts and esters thereof; Acid or its salt and its ester, itaconic acid or its salt and its ester,
Vinylsilyl compounds such as vinyltrimethoxysilane; isopropenyl acetate; N-vinylpyrrolidone;

The polyvinyl ester macromonomer of the present invention is obtained, for example, by reacting a (meth) acrylic halide with a polyvinyl ester polymer having an amino group at one end. Examples of the (meth) acrylic acid halide include (meth) acrylic acid chloride and (meth) acrylic acid bromide. Among them, (meth) acrylic acid chloride is preferable. As a method for synthesizing a polyvinyl ester polymer having an amino group at one end, a vinyl ester or a vinyl ester and a comonomer are added while a thiol in which the amino group portion of a thiol having an amino group is protected in some form is added in a linked manner. To obtain a (co) polymer of a vinyl ester having a protected amino group, and then removing the protecting group to obtain a polyvinyl ester polymer having an amino group at one end. . As the protecting group for the amino group, a t-butyl carbamate group, a benzyl carbamate group, a trifluoroacetamide group, or the like is preferably used because of easy removal of the protecting group.

The reaction between an acrylic acid halide or a methacrylic acid halide and a polyvinyl ester-based polymer having an amino group at one end is carried out by dehydrating the polyvinyl ester-based polymer without using active hydrogen, such as methylene chloride, benzene, toluene, and xylene. , THF or the like. Although a basic substance is used as a collecting agent for the generated hydrogen halide, a substance that may hydrolyze the vinyl ester unit cannot be used, and sodium hydrogen carbonate, pyridine, triethylamine, triethanolamine, etc. are used. You. The reaction is carried out, for example, while slowly dropping an acrylic acid halide or methacrylic acid halide solution into a polyvinyl ester having an amino group at one end and a basic substance, and the total reaction time is 1 to 20 hours, preferably 1 to 10 hours. Time. The reaction temperature at this time is 60 ° C. or less, preferably 40 ° C. or less to suppress side reactions.
20 ° C or higher. The charge ratio of the polyvinyl ester polymer having an amino group at one end to the (meth) acrylic halide is 100 moles of the polyvinyl ester polymer having an amino group at one end (the number of moles of the amino group at one end). On the other hand, the amount of the (meth) acrylic acid halide is 100 to 1000 mol, preferably 100 to 500 mol.

E. Examples Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. “Parts” and “%” in Synthesis Examples and Examples represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Synthesis Example 1 In a container equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a dropping funnel, 9.25 parts of 2-aminoethanethiol,
50 parts of methyl-2-propanol were charged, and nitrogen gas was added to 30 parts.
Degas by bubbling for minutes. While maintaining the temperature of the reactor at 0 ° C., 26.2 parts of di-tert-butyl dicarbonate was slowly added dropwise with stirring, and after completion of the addition, the mixture was heated to reflux for 30 minutes. An aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. After washing with an aqueous sodium hydrogen carbonate solution, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain a crude product. The crude product was purified by distillation under reduced pressure at 0.1 mmHg and 60 ° C. to obtain 16.1 parts of N-tert-butoxycarbonyl-2-aminoethanethiol.

In a reactor equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, 240 parts of vinyl acetate monomer and 60 parts of methanol were added.
Then, nitrogen gas was bubbled for 30 minutes to degas.
Separately, an initial addition solution of thiol obtained by dissolving 0.177 part of N-tert-butoxycarbonyl-2-aminoethanethiol in 50 parts of methanol, N-tert-butoxycarbonyl-2-
Add methanol to 30 parts of aminoethanethiol
Continuous addition of thiol in 50 parts by volume and methanol
Initiator solutions were prepared by dissolving 0.22 parts of 2,2'-azobisisobutyronitrile in 50 parts, respectively, and the mixture was purged with nitrogen by bubbling nitrogen gas.

When the temperature of the reactor was raised and the internal temperature reached 60 ° C., a separately prepared initial addition solution of thiol and an initiator solution were added in this order, and polymerization was started. Immediately, the addition of the thiol continuous addition liquid was started, and the polymerization was continued. The continuous addition of thiol was carried out with the target in the following table as the solid content concentration in the reactor increased with the progress of polymerization. The solid content concentration was checked by sampling.

Polymerization was performed for 3 hours while thiol was continuously added, and the polymerization was stopped by cooling. At this time, the solid content concentration was 35.6%, and the thiol solution continuously added was 28.8 parts by volume. Then 30
The unreacted vinyl acetate monomer was removed while occasionally adding methanol at a temperature of 10 ° C. and a reduced pressure to obtain a polyvinyl acetate methanol solution. A part of the methanol solution was put into ether to recover polyvinyl acetate, and the precipitate was purified by reprecipitation twice with acetone-n-hexane, and then dried at 40 ° C under reduced pressure. This purified polyvinyl acetate, CDC1 ₃ and in the solvent, proton NMR was measured (Nippon Electronic Co., measured by GX-500), N at one end of the number average polymerization degree of 22
-A polyvinyl acetate having a structure having a tert-butoxycarbonylamino group.

To 50 parts of the above polyvinyl acetate, 150 parts of 98% formic acid was added and stirred to obtain a polyvinyl acetate formic acid solution. After leaving this solution at 10 ° C. for 24 hours, it was extracted twice with an aqueous solution of chloroform-sodium chloride, and the chloroform layer was dried over magnesium sulfate. Chloroform was distilled off under reduced pressure, and then dried at 40 ° C. under reduced pressure to obtain polyvinyl acetate. Proton NMR of this polyvinyl acetate was measured using CDCl ₃ as a solvent, and was found to have a number average polymerization degree of 22 and a structure having an ammonium group at one end.

Example 1 Synthesis Example 1 was prepared in a reactor equipped with a stirrer and a dropping funnel.
Polyvinyl acetate with ammonium group at one end
2.86 parts, 10 parts of methylene chloride and 10 parts of a saturated aqueous solution of sodium hydrogencarbonate were taken, and stirred well at room temperature. Subsequently, 0.4 parts of methacrylic acid chloride distilled immediately before and 5 parts of methylene chloride were taken and mixed well.
Dropped over minutes. After completion of the dropwise addition, stirring was continued for another hour at room temperature. Next, a methylene chloride layer was separated by separating the reaction mixture and dried over magnesium sulfate. The solvent was distilled off to obtain crude polyvinyl acetate. After re-precipitating and purifying this polyvinyl acetate twice with acetone-n-hexane,
It dried under reduced pressure at 40 degreeC.

NMR of this purified polyvinyl acetate was measured using CDCl ₃ as a solvent, and was found to be a polyvinyl acetate macromonomer having a number average polymerization degree of 22 and a methacrylamide structure at one end, as shown below. The NMR spectrum is shown in FIG.

GPC was transferred to LC-6A (manufactured by Shimadzu Corporation) using HSG-20.
H, HSG-40H and HSG-60S (manufactured by Shimadzu Corporation) were connected using a THF solvent, a flow rate of 1.0 ml / min, and 25 ° C.
(The same conditions apply to the following measurements), the ratio of the weight-average degree of polymerization to the number-average degree of polymerization was _w / _n = 2.2.

Examples 2 to 5 N-tert-butoxycarbonylamino group at one end having a different number-average degree of polymerization synthesized using N-tert-butoxycarbonyl-2-aminoethanethiol in the same manner as shown in Synthesis Example 1. Using polyvinyl acetate having
A methacrylamide-terminated polyvinyl acetate macromonomer was synthesized in the same manner as in Example 1. Table 1 summarizes the synthesis conditions and results.

Example 6 A number average degree of polymerization having an acrylamide group at one end of 22, and _w / _{n in the same} manner as in Example 1 except that 0.35 part of acrylic acid chloride was used instead of 0.4 part of methacrylic chloride used in Example 1. = 2.2 polyvinyl acetate macromonomer was obtained.

Example 7 Polyvinyl pivalate having an N-tert-butoxycarbonylamino group at one end and an average vinegar degree of polymerization of 48 synthesized by the same method as shown in Synthesis Example 1 except that t-butanol was used as a polymerization solvent was prepared. A vinyl polypivalate macromonomer having a methacrylamide structure at one end and having the following structure was synthesized in the same manner as described in Example 1. Table 2 shows the synthesis conditions and results.

F. Effects of the Invention According to the present invention, a sharp polyvinyl ester-based macromonomer having a polymerization degree distribution excellent in polymerizability derived from the double bond portion having an acrylamide or methacrylamide structure rich in polymerizability is obtained. Can be

Since the polyvinyl ester-based macromonomer of the present invention has a sharp distribution in the degree of polymerization, a graft polymer using the same is more useful than a graft polymer obtained by a conventional method. The macromonomer is also useful as a fiber, a film, a composite material, a photopolymerizable material, and a surface modifier in addition to the raw material of the graft polymer.

[Brief description of the drawings]

FIG. 1 shows an NMR spectrum of the polyvinyl acetate macromonomer obtained in Example 1.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-89208 (JP, A) JP-A-3-174407 (JP, A) JP-A-3-41109 (JP, A) JP-A-61-89 217036 (JP, A) JP-A-59-187003 (JP, A) JP-A-59-187004 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8 / 00,8 / 30,8 / 34 C08F 18/02-18/24 C08F 299/00-299/04

Claims (1)

(57) [Claims] (1) General formula [However, R ^{1 is a} hydrogen atom or a methyl group (X): a linking group bonded to S on the R ² side shown below] (R ² represents an optionally branched alkylene group having 2 to 20 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 4 or less carbon atoms.) (PVES): contains a vinyl ester unit It means a monovalent polyvinyl ester polymer having a number average degree of polymerization of 3 or more (however, excluding those containing a vinyl alcohol unit). ] The polyvinyl ester macromonomer represented by these.