JPH04139203A - Macromonomer - Google Patents

Abstract

PURPOSE:To obtain a macromonomer, composed of substituted acrylamides bound to a polyvinyl ester-based polymer through sulfide bonds, having a sharp distribution of polymerization degree, capable of providing a graft polymer having a highly controlled structure and molecular weight and useful as coatings, etc. CONSTITUTION:An aminothiol compound such as 2-aminoethanethiol is allowed to react with a di-tert. butyl dicarbonate in a solvent to provide N-tert. butoxycarbonyl-2-aminoethanethiol. Vinyl acetate is then polymerized in the presence of the resultant compound using a radical polymerization catalyst to afford polyvinyl acetate having N-tert. butoxycarbonylamino group at one terminal. The terminal protecting group of the polymer is subsequently removed and the obtained compound is allowed to react with methacryloyl chloride to afford the objective macromonomer expressed by formula I [R<1> is H or methyl; X is group expressed by formula II (R<2> is 2-20C alkylene; R<3> is H or <=4C alkyl); PVES is monofunctional polyvinyl ester-based polymer having vinyl ester units and >=3 number-average polymerization degree].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyvinyl ester macromonomer and a polyvinyl alcohol macromonomer.

The polyvinyl ester macromonomer and polyvinyl alcohol macromonomer of the present invention have highly controlled composition, structure, molecular weight, etc., and can be used as raw materials for synthesizing graft polymers.

Graft polymers obtained using the macromonomer of the present invention are more useful in various fields of application, including paints, adhesives, compatibilizers, etc., than graft polymers obtained by conventional methods.

L2LLLL Macromonomers have recently attracted attention as raw materials for the synthesis of highly controlled graft polymers, and an extremely wide variety of macromonomers have been synthesized.

However, when looking at polyvinyl ester macromonomers, only a few examples have been reported, such as polyvinyl acetate macromonomers with terminal olefinic properties (see JP-A-63-95215).

Hereinafter, it will be abbreviated as document (A). ) and styrene-terminated polyvinyl acetate macromonomer (J, Po1yIIle
See rSci, P-C, 25, 175 (1987). Hereinafter, this will be abbreviated as document (B). ), the homopolymerizability and copolymerizability with other monomers are low;
The problem is that it is difficult to obtain polymers with a high degree of polymerization.
child. Furthermore, since the polyvinyl acetate macromonomer disclosed in Document (B) has a cationic group in the linking group, there is a problem in that the scope of its use is greatly limited.

Regarding polyvinyl alcohol-based macromonomers, there are only a few reported examples, even including their precursors. Is it possible to obtain the monomer (see literature (A))? The problem is that the polyvinyl alcohol macromonomer has low homopolymerizability and low copolymerizability with other monomers, making it difficult to obtain a polymer with a high degree of polymerization. was there. In addition, a polyvinyl alcohol-based macromonomer (see literature (B)) obtained by saponifying a styrene-terminated polyvinyl acetate macromonomer (precursor) and a polydimethylalkyl vinyl ether macromonomer (precursor) can be saponified. Polyvinyl alcohol-based macromono 7 (Polymer
Bulletin, 18° 473 (1987)), but the polyvinyl alcohol macromonomer has low copolymerizability with other monomers due to steric hindrance of the linking group derived from the styrene end, and furthermore, In the case of the polyvinyl alcohol macromonomer disclosed in (B), since the linking group portion has cationic properties, there was a problem in that the scope of its use was greatly limited.

Furthermore, polyvinyl alcohol macromonomers having two or more ester groups or amide groups in the linking group moiety (see JP-A-61-89208) are known, but the hydrolysis resistance of the linking group part is low, and There was a problem that polymerizability and copolymerizability with other monomers were also low.

Problems to be Solved by C3 The present invention provides a polyvinyl ester macromonomer and a polyvinyl alcohol macromonomer with excellent polymerizability and a sharp molecular weight distribution.

D Solving the Problem The inventors of the present invention have earnestly studied the above problem and found that the general formula % formula % (1) [R1 hydrogen atom and 2 are methyl groups (X): on the R2 side shown below Linking group (PVES) bonded to S: C-N-R'OR'(R'' represents an alkylene group having 2 to 20 carbon atoms, which may have a branch, and R3 is a hydrogen atom or a group having 4 or less carbon atoms. Represents an alkyl group.) Refers to a monovalent polyvinyl ester polymer containing a vinyl ester unit and having a number average degree of polymerization of 3 or more.] A polyvinyl ester macromonomer represented by the general formula % () [R1 and (X) have the same meaning as in general formula (I).

(PVA): Means a monovalent polyvinyl alcohol polymer containing vinyl alcohol units and having a number average degree of polymerization of 3 or more. ] We have discovered a polyvinyl alcohol-based macromonomer represented by the following and have completed the present invention.

The present invention will be explained in detail below.

The polyvinyl ester macromonomer of the present invention is composed of a polymerizable double bond portion at one end, a polyvinyl ester polymer portion, and a portion connecting the two, and is represented by the above general formula (1).

The polymerizable double bond at one end is acrylamide or methacrylamide, and the double bond and the polyvinyl ester polymer are bonded to each other by a linking group (X) consisting of an amide group and an alkylene group and a sulfur atom. There is. This linking group (X) is (X) : -C-N-R'- 飄OR' (R1 represents an alkylene group having 2 to 20 carbon atoms which may have a branch, and R3 is a hydrogen atom or represents an alkyl group having 4 or less carbon atoms) and is bonded to S on the R1 side. Specific examples of R1 are -(CH,), -1-(CHt)3-1- (cI
(t)a--(CH,),. - etc., and specific examples of R3 include hydrogen, methyl group, ethyl group, propyl group,
Examples include butyl group.

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 even more preferably a ratio of the weight average degree of polymerization to the number average degree of polymerization. is a monovalent polyvinyl ester polymer having a Sharpe polymerization degree distribution of 30 or less, a vinyl ester homopolymer or copolymer, and the content of vinyl ester units is 30 mol% or more, preferably 50 mol% or more. Vinyl ester polymers are preferred. If the number average degree of polymerization of the polyvinyl ester polymer portion exceeds 500, the polymerizability of the obtained polyvinyl ester macromonomer may decrease, or the ratio of the weight average degree of polymerization to the number average degree of polymerization of the polyvinyl ester polymer may decrease. (hereinafter sometimes abbreviated as polymerization degree distribution or pv/Pn) exceeds 3.0, there is a problem that the characteristics of the graft polymer obtained from the polyvinyl ester macromonomer of the present invention are not sufficiently expressed. may occur. The degree of polymerization distribution here is based on GPC measurement (measurement conditions: tetrahydrofuran (hereinafter abbreviated as THF) solvent, flow rate 1.0 ml/lin, 25° C.).

Further, even if the content of vinyl ester units in the polyvinyl ester polymer is 30 mol % at the end, the characteristics of the graft polymer obtained from the polyvinyl ester macromonomer of the present invention may not be sufficiently exhibited.

Vinyl ester (hereinafter sometimes abbreviated as YES) units constituting the polyvinyl ester polymer portion of the present invention include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl valerate, and vinyl ester.゛′Vinyl purinate, vinyl versatate,
Examples include units consisting of vinyl laurate, vinyl stearate, vinyl benzoate, vinyl trifluoroacetate, vinyl trichloroacetate, and the like. When the polyvinyl ester polymer is a copolymer, the comonomer (hereinafter sometimes abbreviated as CMI) is not particularly limited and is selected from units that can be introduced by copolymerization. Examples of such comonomers (CMI) include the following. Namely, olefins such as ethylene, propylene, niebutene, and isobutyne, acrylic acid or its salts, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, and i-butyl acrylate. , t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, acrylic esters such as octadenyl acrylate, methacrylic acid or its salts, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacrylic acid -Propyl, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, methacrylic acid esters such as octadecyl methacrylate, acrylamide, N-methylacrylamide, N- Acrylamide derivatives such as ethyl acrylamide, N,N-dimethylacrylamide, diacetone acrylamide, acrylamide propanesulfonic acid or its salt, acrylamide propyl dimethylamine or its salt and its quaternary salt, N-methylolacrylamide or its derivative, methacrylamide, Methacrylamide such as N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid or its salt, methacrylamidepropyldimethylamine, its salt and its quaternary salt, N-methylolmethacrylamide or its derivative Derivatives, hinyl ethers such as methyl hinyl ether, ethyl vinyl ether, n-propyl vinyl ether, 1-propyl vinyl ether, n-butyl vinyl ether, -butyl vinyl ether, t-butyl vinyl ether, dodenruhinyl ether, stearyl hinyl ether, acrylonitrile, methacryl Nitriles such as nitrile, vinyl chloride, vinylidene chloride, vinyl fluoride,
Vinyl halides such as vinylidene fluoride, allyl compounds such as allyl acetate and allyl chloride, maleic acid or its salts and its esters, fumaric acid or its salts and its esters, itaconic acid or its salts and its esters, vinyl trimethoxylate These include vinylsilyl compounds such as nosilane, isopropenyl acetate, and N-vinylpyrrolidone.

The polyvinyl ester macromonomer of the present invention is obtained, for example, by reacting (meth)acrylic acid halide with a polyvinyl ester polymer having an amino group at one end. Examples of (meth)acrylic acid halides include (meth)acrylic acid bromide, and (meth)acrylic acid chloride is particularly preferred. A method for synthesizing a polyvinyl ester polymer having an amino group at one end is to synthesize a vinyl ester or a vinyl ester with a comonomer while continuously adding a thiol in which the amino group of the thiol that grows the amino group is protected in some way. A method is to obtain a (co)polymer of vinyl ester having a protected amino group by polymerizing with and then removing the protecting group to obtain a polyvinyl ester polymer having an amino group at one end. Can be mentioned. As the protecting group for the amino group, t-butyl carbamate group, benzyl carbamate group, trifluoroacetamide group, etc. are preferably used because they are easy to remove the protecting group.

The reaction between acrylic acid halide or methacrylic acid halide and a polyvinyl ester polymer having an amino group at one end can be carried out using a solvent that does not have active hydrogen and has well dehydrated the polyvinyl ester polymer, such as methylene chloride, benzene, toluene, or a kiln. , THF or the like. Basic substances are used as scavengers for the generated hydrogen halide, but substances that may hydrolyze vinyl ester units cannot be used, and sodium bicarbonate, pyridine, triethylamine, triethanolamine, etc. are used. Ru. The reaction is carried out, for example, by 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. It's time. The reaction temperature at this time is 60°C or lower, preferably 40°C or lower, and 20°C or higher in order to suppress side reactions. The charging ratio of the polyvinyl ester polymer having an amino group at one end and the (meth)acrylic acid 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). (meth)acrylic acid halide 100-10
00 mol, preferably 100 to 500 mol.

The polyvinyl alcohol macromonomer, which is the next aspect of the present invention, is composed of a polymerizable double bond portion at one end, a polyhinyl alcohol polymer portion, and a portion connecting the two, and has the general formula (n ).

The polymerizable double bond portion at one end is acrylamide or methacrylamide, and the double bond and the polyvinyl alcohol polymer are bonded by a linking group (X) consisting of an amide group and an alkylene group and a sulfur atom. ing. As this linking group (X), the same one as in the above general formula (I) is used.

The polyvinyl alcohol polymer (PVA) portion has a number average degree of polymerization of 3 or more, preferably 3 to 500, more preferably 5 to 300, and even more preferably a ratio of the average degree of polymerization to the number average degree of polymerization. It is a polyvinyl alcohol polymer of Ifa having a sharp polymerization degree distribution of 30 or less, and the content of vinyl alcohol units is 10 mol% or more, preferably 30 mol% or more, more preferably 5
It is a vinyl Q real alcohol-based polymer containing 0 mol% or more. The number average degree of polymerization of the polyvinyl alcohol polymer part is 50
If it exceeds 0, the polymerizability of the obtained niborivinyl alcohol macromonomer may decrease, or the ratio of the weight average degree of polymerization to the number average degree of polymerization (hereinafter referred to as polymerization degree distribution or FW/ If Pn (sometimes abbreviated as Pn) exceeds 3.0, the characteristics of the graft polymer obtained from the polyvinyl alcohol macromonomer of the present invention may not be sufficiently expressed, and one or two problems may occur. Here, the polymerization degree distribution (Y, G for a polymer that acetylated vinyl alcohol units to vinyl acetate units)
This is based on PC measurement (measurement conditions: THF solvent,
Flow rate 1.0+*l/win.

25℃). Furthermore, when the content of vinyl alcohol units in the polyvinyl alcohol polymer is less than 10 mol %, the characteristics of the graft polymer obtained from the polyvinyl alcohol macromonomer of the present invention may not be fully expressed.

Units other than vinyl alcohol units when the polyvinyl alcohol polymer (PvA) is a copolymer include:
Vinyl ester (YES'I unit and comonomer (CMI) in the polyvinyl ester macromonomer column)
) units are listed.

The polyvinyl alcohol macromonomer of the present invention can be obtained, for example, by solvolyzing the above-mentioned polyvinyl ester macromonomer having a (meth)acrylamide group at one end. There are no particular restrictions on the reaction conditions for solvolysis, but alcohololysis using an alkali catalyst is recommended in order to prevent hydrolysis of the amide bond that connects the terminal double bond and the polyvinyl alcohol polymer. Preferably! La0K, OE[, CEI-ONa
, CtElaONa.

Methanolysis using CFI, OK C, El, OK is particularly preferred. The amount of alkali catalyst during solvolysis is set at 0.02 to 200 moles per 100 moles of vinyl ester units to be solvolyzed, and the saponification temperature is set between room temperature and 120°C.

The present invention will be explained in more detail with reference to Synthesis Examples and Examples below, but the present invention is not limited thereto in any way. In addition, "part" and "%" in synthesis examples and examples
represent "parts by weight" and "% by weight", respectively, unless otherwise specified.

Synthesis Example I 925 parts of 2-aminoethanethiol, 2-
50 parts of methyl-2-propertool was charged and degassed by bubbling nitrogen gas for 30 minutes.

The temperature of the reactor was kept at 0°C, and under stirring, the temperature of the reactor was kept at 0°C.
262 parts of butyl carbonate was slowly added dropwise, and after the addition was completed, the mixture was heated under 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 bicarbonate solution, it was dried over magnesium sulfate, and the solvent was distilled off to obtain a crude product. The crude product was purified by vacuum distillation at 60°C at O, lmmHg to obtain N-tart-butquine carbonyl-2.
-16.1 parts of aminoethanethiol were obtained.

240 parts of vinyl acetate monomer and 6 parts of methanol were placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer.
0 parts was charged and degassed by bubbling nitrogen gas for 30 minutes. Separately, N-tert-butoxycarbonyl-2-
An initial addition solution of thiol in which 0.177 parts of aminoethanethiol was dissolved in 50 parts of methanol, and methanol was added to 30 parts of N-tart-butoxycarbonyl-2-aminoethanethiol to make the total amount 50 parts by volume.Continuous addition of thiol. An initiator solution was prepared by dissolving 0.22 parts of 2,2'-azobisisobutyronitrile in 50 parts of methanol and arsenic substitution was performed by bubbling nitrogen gas.

The temperature of the reactor was started to rise, and when the internal temperature reached 60° C., a separately prepared initial addition solution of thiol and an initiator solution were added in this order to start polymerization.

Immediately, continuous addition of the thiol solution was started to continue polymerization. Continuous addition of thiol was carried out with the aim of achieving the values shown in the table below in proportion to the increase in solid content concentration in the reactor as the polymerization progressed. The solid content concentration is San solid content (%')
10 20 30 40 Continuous addition amount (811) 7.0 14.1 21,5 29
．． Polymerization was carried out for 3 hours while continuously adding 2thiol, and the polymerization was stopped by cooling. The solid content concentration at this time was 356%,
The continuously added thiol solution was totaled at 28.8 parts by volume.

Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30° C. to obtain a methanol solution of polyvinyl acetate. A part of this methanol solution was poured into ether to recover polyvinyl acetate, which was purified by reprecipitation twice with acetone-n-hexane.
It was dried under reduced pressure at 0°C. When this purified polyvinyl acetate was measured by proton NMR (measured with G
It was a polyvinyl acetate with a structure having a -butoxycarbonylamino group.

150 parts of 98% formic acid was added to 50 parts of the above polyvinyl acetate and stirred to obtain a formic acid solution of polyvinyl acetate. This solution was left at 10° C. for 24 hours, extracted twice with a chloroform-sodium chloride aqueous solution, and the chloroform layer was dried with magnesium sulfate.

After chloroform was distilled off under reduced pressure, polyvinyl acetate was obtained by drying under reduced pressure at 40°C. Regarding this polyvinyl acetate, proton NMR was performed using CDCl3 as a solvent.
As a result of measurement, the polyvinyl acetate had a number average degree of polymerization of 22 and had an ammonium group at one end.

Example 1 Polyvinyl acetate 2 having an ammonium group at one end as shown in Synthesis Example 1 was placed in a reactor equipped with a stirrer and a dropping funnel.
．． 86 parts of the mixture, 10 parts of methylene chloride, and 10 parts of a saturated aqueous sodium bicarbonate solution were taken and stirred well at room temperature. Subsequently, 0.4 parts of methacrylic acid chloride distilled just before and 5 parts of methylene chloride were taken and mixed well, and then added dropwise in one portion while stirring at room temperature. After the addition is complete, continue stirring at room temperature for another hour. Next, the reaction mixture was subjected to liquid separation to separate a methylene chloride layer, which was dried over magnesium sulfate, and then the solvent was distilled off to obtain crude polyvinyl acetate.

This polyvinyl acetate was purified by reprecipitation twice with acetone-n-hexane, and then dried under reduced pressure at 40'C.

When NMR was measured using CDCl3 as a solvent for this purified polyvinyl acetate, it was found to be a polyvinyl acetate macromonomer having the following structure with a number average degree of polymerization of 22 and a methacrylamide structure at one end.

The NMR spectrum is shown in FIG.

CHl CH, =C C-NH-CH2CH*-SBH, -CH), -H00
COCH.

In addition, GPC, LC-6A (manufactured by Takasugi Seisakusho (Aji)) 1
．． =H3G-20H, H5G-40H and HsG80
5 (manufactured by Takasu Seisakusho C Co., Ltd.) using a device connected to
THF solvent, flow rate 1.0ml/win, measured at 25°C (
The following measurements were also carried out under the same conditions), and the ratio of the weight average degree of polymerization to the number average degree of polymerization was P,/P, = 2.2.

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

2) Methacrylic acid chloride Example 6 Except for using 0.35 parts of acrylic acid chloride instead of 04 parts of methacrylic acid chloride used in Example 1,
In the same manner as in Example 1, a polyvinyl acetate macromonomer having an acrylamide group at one end, a number average degree of polymerization of 22, and PW/p n = 2.2 was obtained.

Example 7 Synthesis Example 1 except that t-butanol was used as the polymerization solvent
It was synthesized in the same manner as shown in , and the r co number average polymerization degree was 48.
A polyvinyl pivalate macro having the following structure is prepared by growing a methacrylamide structure at one end in the same manner as shown in Example 1 using polyhinyl pivalate having an N-tert-butquine carbonylamino group at one end. Synthesize monomer f2. Synthesis conditions and results are shown in Table 2.

Hs H3O-C-CB.

Hs Example 8 1.91 parts of the polyvinyl acetate macromonomer having methacrylamide at one end as shown in Example 11. 30 parts of methanol was added to form a solution. Separately, a solution was prepared in which 0.18 parts of sodium hydroxide was dissolved in 10 parts of methanol, and both solutions were mixed. After being allowed to stand at room temperature for one day, the precipitated solid was gamma-filtered, washed with Soxhlet with methanol all day and night, and then vacuum-dried at 40°C. Proton NMR measurements of this polyvinyl alcohol using DMS○-d6 as a solvent revealed that it was a polyvinyl alcohol macromonomer having a methacrylamide structure at one end. FIG. 2 shows the NMR spectrum. Further, 7 parts of acetic anhydride and 3 parts of pyridine were added to 1 part of the polyvinyl alcohol macromonomer, and the mixture was heated at 110° C. for 5 hours to perform reacetylation. The obtained polyvinyl acetate was converted into CDC+,
The number average degree of polymerization was 22 when dissolved in and measured by proton NMR.

Example 9~! 2 The polyvinyl acetate macromonomers shown in Examples 2 to 5 were saponified in the same manner as in Example 8 to obtain a polyvinyl alcohol macromonomer having a methacrylamide group at one end. The results are summarized in Table 3.

According to the present invention, a polyvinyl ester-based macromonomer and a polyvinyl alcohol-based macromonomer with a 7-yave polymerization degree distribution and excellent polymerizability derived from the fact that the double bond portion has an acrylamide or methacrylamide structure with high polymerizability. is obtained.

Since the polyvinyl ester macromonomer and polyvinyl alcohol macromonomer of the present invention have a sharp polymerization degree distribution, a graft polymer using them is more useful than a graft polymer made by conventional methods.

The macromonomer is useful not only as a raw material for graft polymers but also as fibers, films, composite materials, photopolymerizable materials, and surface modifiers.

[Brief explanation of the drawing]

FIG. 1 shows the NMR spectrum of the polyvinyl acetate macromonomer obtained in Example 1. FIG. 2 shows the NMR spectrum of the polyvinyl alcohol macromonomer obtained in Example 8.

Claims (2)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [However, R^1: Hydrogen atom or methyl group (X): Linking group (R ^2 represents an alkylene group having 2 to 20 carbon atoms which may have a branch, and R^3 represents a hydrogen atom or an alkyl group having 4 or less carbon atoms.) (PVES): Contains a vinyl ester unit. Each term means a monovalent polyvinyl ester polymer having a number average degree of polymerization of 3 or more. ] A polyvinyl ester macromonomer represented by: (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [However, R^1 and (X): have the same meaning as in the general formula (I) described in claim 1. (PVA): Means a monovalent polyvinyl alcohol polymer containing vinyl alcohol units and having a number average degree of polymerization of 3 or more. ] A polyvinyl alcohol macromonomer represented by: