JPH04132706A - Production of terechelic polymer having terminal hydroxyl groups - Google Patents

Abstract

PURPOSE:To inexpensively obtain the title polymer for coating, etc., capable of carrying out terminal acryloylation by polymerizing a monomer in the presence of a specific halogen compound and polymerization initiator to afford a halogen-ended polymer, converting the terminal group into hydroxyl group by a substitution reaction. CONSTITUTION:(C) A polymerizable monomer (e.g. butyl acrylate) is polymerized in the presence of (A) a halogenated compound (e.g. methane diiodide) expressed by the formula (R<1> is 1-8C divalent hydrocarbon; X<1> and X<2> are bromine or iodine) and (B) polymerization initiator [e.g. 2,2'-azobis(4-methoxy-2,4- dimethylvaleronitrile)] at an amount of the component C which is 0.01-10 times (by mol) larger than amount of the component A to afford a halogen-ended terechelic polymer and then the terminal group of the polymer is converted into hydroxyl group by utilizing a substitution reaction using an aqueous solution of sodium hydroxide, etc., to provide the objective hydroxyl group-ended terechelic polymer.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a polymer that itself has a terminal reactive group and is very useful as a raw material for polyurethane resins, polyester resins, paints, adhesives, sealants, etc. The present invention also relates to a method for producing a hydroxyl-terminated telechelic polymer that can be easily converted into a vinyl crosslinking agent having a terminal functional group such as a vinyl group or (meth)acryloyl group.

(Prior Art and Problems to be Solved by the Present Invention) Telekeric polymers ideally have one functional group at each end, and therefore, each N84 resin such as polyurethane resin or epoxy resin When used as a raw material, it is reliably incorporated into the m-finger structure without any unreacted substances that would affect the physical properties of the material, and the distance between reaction points (between crosslinking points) is constant to create a uniform product. It has the great advantage of being able to fully exploit the characteristics of telekeric polymers, and is therefore extremely useful as a raw material for various resins, paints, adhesives, sealants, etc. Among them, hydroxyl group-terminated telechelic polymers are industrially very useful as raw materials for polyurethane resins, polyester resins, etc. Telechelic polymers currently used industrially include polyether-based, Polyester-based materials are common, but
It still has drawbacks such as poor weather resistance and water resistance.

On the other hand, vinyl-based telechelic polymers are not easy to synthesize industrially (some polybutadiene telechelic polymers are known, but these do not fully overcome the drawbacks of polyether- and polyester-based telechelic polymers). In particular, it is thought that the disadvantages of polyether-based and polyester-based telechelic polymers can be solved by acrylic-based telechelic polymers, but polar polymerizable monomers such as acrylic esters and methacrylic esters At present, there is no industrial method for producing telechelic polymers that uses biochemistry.

Halogen atoms such as chlorine, bromine, and iodine are highly reactive functional groups, and a halogen-terminated telechelic polymer having such halogen atoms at both ends of the polymer is used as an intermediate to hydrolyze the terminal halogen atoms. A telechelic polymer having a hydroxyl group at its terminal can be easily synthesized by utilizing a substitution reaction with a diol compound, an amine compound having a hydroxyl group, a carboxylate compound, or the like.

A conventional method for producing a vinyl polymer having halogen atoms at both ends of the polymer is a telomolization reaction using carbon tetrachloride or the like as a chain transfer agent.

A typical example is the polymerization of ethylene using carbon tetrachloride. The polymer obtained by this reaction is CI (CH2-CHz)--CC1 year old (n=1~
10), and has halogen atoms at both ends, but the number of atoms at the ends is 11 [1
, 3-biased and heterogeneous, and even if a hydrolysis reaction or a substitution reaction with a diol compound, an amine compound having a hydroxyl group, a carboxylate compound, etc., the 3-terminus at one end
Of the halogen atoms, those in which only one reacted, those in which two reacted, those in which all three reacted, and the structure after the reaction,
becomes non-uniform, making it impossible to synthesize an ideal telechelic polymer.

The object of the present invention is to create a polymer which itself has a terminal reactive group and which is very useful as a material for polyurethane 11 resin, polyester resin, paint, adhesive wound, sealing material, etc., but which is complicated and difficult to synthesize. A method for easily and inexpensively producing a halogen-terminated telechelic polymer synthesized by a telomolization reaction using a halogen-terminated telechelic polymer as an intermediate, and converting the terminal A halogen atom into a hydroxyl group using a substitution reaction. Our goal is to provide the following.

(Means and effects for solving the problem) 2s: The inventors (;, in the presence of a compound containing two halogen atoms consisting of bromine δ and/or: = iodine per 1,000 molecules, and a polymerization initiator, The halogen-terminated telechelic polymer obtained by polymerizing a polymerizable monomer is hydrolyzed or subjected to a substitution reaction with a diol compound, an amine compound having a hydroxyl group, a carboxylate compound, etc., at the end of the halogen-terminated telechelic polymer. The present inventors have discovered that by carrying out this method, it is possible to easily and inexpensively synthesize a hydroxyl group-terminated telechelic polymer even when the polymerizable monomer contains polar monomers such as acrylic esters and methacrylic esters, and the present invention has been achieved. It is something.

That is, the present invention relates to the general formula (I) RXIχt (1) (wherein R is a C+ to C- divalent hydrocarbon group, X-) (
Each i is independently bromine or iodine. ) and a polymerization initiator (b).
0.01 to 0.01 to the halogen compound (a) in the presence of
A hydroxyl group characterized by polymerizing 10 times the molar amount of the polymerizable monomer (C) to obtain a halogen-terminated telechelic polymer, and then converting the halogen-terminated telechelic polymer into a hydroxyl group using a substitution reaction. This is a method for producing terminal telechelic polymers.

Examples of the halogen compound (&) represented by the general formula (1) used in the present invention include dibromomethane, 1.1-
Dibromoethane, 1,2-dibromoethane, 1,2-dibromopropane, 1,3-dibromopropane, 1.3
-dibromobutane, 1゜4-dibromobutane, 1,5
-Dibromopentane.

1.6-dibromohexane, 1.7-dibromohebutane, 1.8-dibromooctane, 1.2-dibromoethylene, 2.3-dibromopropene, short methane, 1
, 1-short ethane, 1,2-short ethane,
1.2-short ethylene, bromoiodomethane, 1
-Bromo-2-iodoethane, etc., and a mixture of 1 N or more of these can be used.

Among these, iodine compounds such as short methane, 1,1-diiodoethane, 1,2-di=-doethane, and 1,2-diiodoethylene have large linked flN kinetic constants and are highly efficient in telomerization. is very preferable because the number of terminal halogen functional groups (Fn (X)) of the resulting teleclick polymer becomes high (approaching 2.0).

Further, examples of the polymerizable monomer (c) used in the present invention include acrylic acid, ester acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate,
2-ethylhexyl acrylate, acrylic dodecyl,
Stearyl acrylate.

2-hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, 2-N acrylate
, N-dimethylaminoethyl and its quaternary salts, acrylic esters such as monoacrylic ester of polyethylene oxide; methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, M2-ethylhexyl methacrylate , dodecyl methacrylate, stearyl methacrylate, 2'=dromocynityl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, methacrylic H2-N, N-dimethylaminoethyl and its quaternary salt, monomethacrylate ester of polyethylene oxide, etc. Methacrylic acid ester top: maleic acid,
Maleic anhydride, monoalkyl esters and dialkyl esters of maleic acid; Fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; Styrene derivatives such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, styrene sulfonic acid; Maleimide Maleimide derivatives such as , methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide: Nitrile group-containing polymerizable base material WL such as acrylonitrile and methacrylonitrile:
Amide group-containing polymerizable monomers such as acrylamide and methacrylamide: vinyl acetate, propionic vinyl, vinyl pivalate, acetic acid,! Vinyl esters such as vinyl fragrant, butadiene, isoprene, etc. 2 Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. These 11 or 21! i
A mixture of the above can be used.

Among these, when acrylic esters and methacrylic esters are used, telechelic polymers with good weather resistance and water resistance that cannot be obtained with polyether-based and polyester-based telechelic polymers can be obtained. It is preferable to use acid esters and/or methacrylic esters as essential, and it is more preferable to use them in an amount of 50 to 100% by weight in the polymerizable monomer (C).

The polymerizable monomer (C) is 0 with respect to the halogen compound (a)
．． Must be used in an amount of 0.1 to 10 times the molar amount,
When the amount used is less than 0.01 times the mole, the progress of polymerization is hindered and the polymerization rate becomes low.

Furthermore, if the amount exceeds 10 times the mole, chain transfer will not occur sufficiently, and the number of terminal halogen functional groups in the resulting polymer will decrease. Preferably;=,0. It ranges from 1 to 5 fmol.

The polymerization initiator (b) can be used without any restriction as long as it is conventionally used for radical polymerization of polymerizable monomers. The amount used can be in a wide range depending on the properties of the obtained telechelic polymer, but the molar ratio of halogen compound (a)/polymerization initiator (b) is from 50 to
It is preferable to use it in an amount in the range of 500. If the molar ratio is less than 50, the chain transfer to the halogen compound (a) will be insufficient, and the number of terminal halogen functional groups in the obtained polymer will decrease, or This may hinder the progress of polymerization and reduce the polymerization rate.

During polymerization, the halogen compound (a), the polymerizable monomer (
c) A solvent may be freely added in addition to the polymerization initiator (b) as required. However, it is not preferable to use a large amount of a solvent with a large chain transfer constant, and if the chain transfer constant is lXl0-' or more, as this will reduce the number of terminal halogen functional groups in the resulting polymer.The polymerization temperature can be selected arbitrarily, but 20~120℃ is preferable, 20~80℃
℃ is further Ti=i:L, and even when bimolecular termination occurs, the formation of terminal 21i bonds in the polymer due to disproportionation termination is avoided, and the number of terminal halogen functional groups is reduced by recombination termination. In order to efficiently introduce one halogen molecule to both ends of the polymer, a temperature of 20 to 50°C is particularly preferable.

Specific examples of the polymerization initiator (b) include 22°-azobisisobutyronitrile, 2,2°azobis(2,4
-dimethylvaleronitrile), 2.2°-azobis(4
-methoxy-2,4-dimethylvaleronitrile), 4,
Azo initiators such as 4′-azobis(4-cyanopentanoic acid); peroxides such as lauroyl peroxide, benzoyl peroxide, isobutyryl peroxide, tert-butyl pivaloyl peroxide, di-tert-butyl peroxide, etc. Redox type initiators such as Fe”°/hydrogen peroxide, hydrogen peroxide/ascorbic acid, benzoyl peroxide/dimethylaniline, etc., and these can be used alone or in a mixture of two or more. However, since it is more preferable to carry out the polymerization at a low temperature, among these initiators, 2.2'-azobis(4-methoxy-24-dimethylvaleronitrile), imbutyryl peroxide, and tert-butyl peroxide are used. More preferred are pivaloyl, redox initiators, and the like.

In the method of the present invention, a terminal halogen atom of a halogen-terminated telechelic polymer is converted into a hydroxyl group using a substitution reaction. Although there are no particular restrictions on the speciation of the f-conversion reaction, the following four methods are advantageous in terms of reaction efficiency and resistance to cleavage of the main chain of the telechelic polymer or gla.

1. Hydrolysis reaction 2. Substitution reaction with a diol compound 3. Substitution reaction with an amine compound having a hydroxyl group 4. Substitution reaction with a carboxylate compound having a hydroxyl group Each of the above-mentioned substitution reactions will be described in detail below.

The basic catalyst (d) used for the hydrolysis of the terminal halogen atoms of the halogen-terminated telechelic polymer may be any basic compound that is not used for the hydrolysis of general Ikuto halides, but sodium hydroxide may be used. , potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like are preferred, and these compounds can be used alone or in a mixture of 2ffi or more.

The molar ratio of the basic catalyst (d) and the terminal halogen atom of the halogen-terminated telechelic polymer during hydrolysis of the terminal halogen atom of the halogen-terminated telechelic polymer is such that the basic catalyst (d) is the halogen-terminated telechelic polymer. There is no problem if the amount of the basic catalyst (d) is at least equimolar to the terminal halogen atom of the halogen-terminated telechelic polymer, but if the amount of the basic catalyst (d) is too small relative to the terminal halogen atom of the halogen-terminated telechelic polymer, hydrolysis will not proceed quantitatively; If the amount is too large, there is a risk that in addition to the terminal halogen atoms of the halogen-terminated telechelic polymer, the side M of the polymer may be hydrolyzed.
Specifically, the amount of basic catalyst (d) added to the terminal halogen atom of the polymer is preferably 1 to 10 times the molar amount,
More preferably, it is 3 to 5 times the molar amount.

In addition, there are no particular restrictions on the solvent for hydrolysis of the terminal halogen atom of the halogen-terminated telechelic polymer, but a solvent that can react with the halogen-terminated telechelic polymer basic catalyst (d) and water to a nearly uniform state. egoism,
Specifically, highly polar substances such as acetone, tetrahydrofuran, and dioxane are preferable. However, it is preferable not to use alcohols as they may cause competitive substitution reactions to generate ether bonds and reduce the number of terminal functional groups. Furthermore, additives such as phase transfer catalysts may be freely used in the hydrolysis reaction.

The temperature during hydrolysis of the terminal halogen atom of the halogen-terminated telechelic polymer can be selected arbitrarily, but it is between 20°C and 10°C.
0°C is preferable, and 20°C to 60°C is more preferable.

General formula (II) HOR'OH used for substitution reaction with terminal halogen atom of halogen-terminated telechelic polymer
(n) (In the formula, R2 is a divalent hydrocarbon group of 01-〇, which may have a substituent.) and/or general formula (m) HO-(R2-0)Il-H (m) (wherein, R2 is a divalent hydrocarbon group from 01 to C-th,
n is an integer from 1 to 1000. ) The diol compound (f) represented by ethylene glycol, 1,3
-propanediol, 1,2-propanediol,
1.4-butanediol, 1゜3-butanediol,
1,6-hexanediol.

1.8-octanediol, 1.10-decanediol, 1.12-dodecanediol, 1.18-octadecanediol, bisphenol, hydrogenated products of bisphenol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, etc. Examples include polyethylene glycol, poly-10 pyrene glycol, polytetramethylene glycol, etc., and these can be used alone or in a mixture of two or more.

The basic catalyst (e) used in the substitution reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and a diol compound may be any basic compound used in the substitution reaction between a wired halide and an alcohol. Compounds containing alkali metals such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, and potassium carbonate are preferred, and these compounds can be used alone or in a mixture of two or more.

ff of one terminal halogen of the halogen-terminated telechelic polymer and the diol compound (f)! The reaction amount ratio does not matter as long as the diol compound (f) is equimolar or more to the halogen atom at the end of the polymer. In order to avoid an increase in the molecular weight of the resulting polymer, it is preferable that the diol compound (f) be present in excess of the halogen atom at the end of the polymer. (f) The amount of additive is preferably at least 3 times the molar amount, and more preferably at least 10 molar amount.

There is no particular restriction on the solvent used in the one-flex reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and the diol compound (f), but the solvent used in the single-flex reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and the diol compound (f) is not particularly limited. It is best to use a substance that can be made into a more homogeneous state during the reaction, specifically highly polar substances such as acetone, tetrahydrofuran, and dioxane. It is preferable not to use it too much since it may reduce the number of groups.Furthermore, it is free to add a phase transfer catalyst or the like to the substitution reaction.

The temperature during the substitution reaction between the terminal A halogen of the halogen-terminated telechelic polymer and the diol compound (f) can be selected arbitrarily, but is preferably 20°C to 100°C, and 20°C to 60°C.
is even more interesting.

One formula (IV), R4NHR, used for the monovalent reaction with a terminal halogen atom of a halogen-terminated telechelic polymer.
5OH(IVH(IV) (wherein, R4 is hydrogen or an alkyl group of 01 to 01,
ps is a divalent hydrocarbon group of 01 to C8. ) The hydroxyl group-containing compounds (g) include ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, 3-
Hydroxypropylamine, N-methyl-3-hydroxypropylamine, 4-hydroxybutylamine, N-
Methyl-4-hydroxybutylamine, 6-hydroxyhexylamine, N-methyl-6-hydroxyhexylamine, 8-hydroxyoctylamine, N-methyl-
Examples include 8-hydroxyoctylamine, 12-hydroxydodecylamine, N-methyl-12-hydroxydodecylamine, 18-hydroxyoctadecylamine, N-methyl-18-hydroxyoctadecylamine, and one or more of these Can be used in mixtures.

The hydroxyl group-containing amine compound (g) may be a primary or secondary amine compound, but the amine group at the end of the polymer generated by the ta reaction may further undergo a substitution reaction with a halogen atom at the end of the polymer to increase the molecular weight of the resulting polymer. To avoid this, the hydroxyl group-containing amine compound (g) must be
An amine compound is preferred.

In addition, the molar ratio of the terminal halogen atom of the halogen-terminated telechelic polymer and the hydroxyl group-containing amine compound (g) during the substitution reaction may be at least equimolar to the terminal halogen atom of the polymer. However, in order to avoid high molecular weight of the resulting polymer caused by the substitution reaction of the hydroxyl group at the end of the polymer generated by the substitution reaction with the halogen atom at the end of the polymer, the hydroxyl group-containing amine compound (g) must be It is preferable that it is present in excess. Specifically, the amount of the hydroxyl group-containing amine compound (g) added is preferably at least 3 times the molar amount, more preferably at least 10 molar amount, relative to the terminal halogen atom of the polymer.

In addition to these, additives such as a solvent, a catalyst, and a phase transfer catalyst may be freely used in the substitution reaction of the Song-tian halogen of the halogen-terminated teleclick polymer and the hydroxyl group-containing amine compound (g).

The reaction temperature for the substitution reaction between the terminal halogen atom of the halogen-terminated telechelicef polymer and the hydroxyl group-containing amine compound (g) can be arbitrarily selected, but is preferably 20°C to 10°C.
0°C, more preferably 20°C to 60''C.

General formula (V) HOR@C00 used for substitution reaction with terminal halogen atom of halogen-terminated telechelic polymer
The hydroxyl group-containing carboxylate compound (h) represented by M (V) (in the formula, R is a divalent hydrocarbon group of 01 to C11, and M is an alkali metal) includes hydroxyacetic acid, 2 -Hydroxypropionic acid, 3-hydroxypropionic acid, 2
-Hydroxy-2-methylpropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisovaleric acid, 2-hydroxyisovaleric acid, 2-hydroxyoctanoic acid, 3-hydroxyoctane acid, 2-hydroxydecane Acid, 3-hydroxydodecanoic acid, 2-hydroxydodecanoic acid, 3-hydroxydodecanoic acid, 2-hydroxyundecanoic acid, 3-hydroxyundecanoic acid, 2-hydroxydodecanoic acid, 3-hydroxydodecanoic acid, 2-hydroxytridecanoic acid acid, 3-hydroxytridecanoic acid,
2-hydroxytetradecanoic acid, 3-hydroxytetradecanoic acid, 2-hydroxypentadecanoic acid, 3-hydroxypentadecanoic acid, 2-hydroxyhexadecanoic acid,
Examples include alkali metal salts such as sodium and potassium such as 3-hydroxyhexadecanoic acid, 12-hydroxystearic acid, and 12-hydroxyoleic acid.
These 11it or a mixture of two or more can be used.

The molar ratio of the terminal halogen atom of the halogen-terminated teleclick polymer and the hydroxyl group-containing carboxylate compound (h) during the substitution reaction is as long as the hydroxyl group-containing carboxylate compound (h) is equal mole or more to the polymer terminal halogen atom. The solvent used in the substitution reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and the hydroxyl group-containing carboxylate compound (h), which may be used in a substitution reaction of the terminal halogen atom of the halogen-terminated telechelic polymer, is preferably 3 times or more, more preferably 5 times or more in molar amount. Although there is no particular restriction on the halogen-terminated telechelic polymer and the hydroxyl group-containing carboxylic acid salt compound (h), it is preferable to use a material that can make the halogen-terminated telechelic polymer and the hydroxyl group-containing carboxylic acid salt compound (h) more homogeneous during the reaction. It is preferable to use solvents with high polarity or mixed solvents of these highly polar solvents and water.However, it is preferable not to use alcohol as it may cause a competitive substitution reaction to generate ether bonds and reduce the number of terminal functional groups. is preferable, and
Additives such as catalysts and phase transfer catalysts may be used freely in the substitution reaction.

The reaction temperature for the substitution reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and the hydroxyl group-containing carboxylate compound (h) is arbitrary! 20℃, preferably 20℃
-100°C, more preferably 20°C - 60°C.

The number of functional groups per molecule is 2.0 (1), but even if the number of functional groups is less than 2.0, the industrial lr applicability is not lost;
If the average number of terminal hydroxyl functional groups in the molecule is greater than about 1.8, it is possible to exhibit almost ideal physical properties. Furthermore, if the average number of terminal hydroxyl groups is 1.5 or more, it can be preferably used in many industrial fields, and if it is larger than 1°0, it will exhibit characteristics as a telechelic polymer to some extent. and has industrial value.

The hydroxyl-terminated telechelic polymer of the present invention utilizes the reactivity of its terminal hydroxyl groups to produce polyurethane resins, polyester resins, and more! In addition to being used for various purposes as a raw material for ll materials, adhesives, and sealing materials, it can also be used as a polymerizable unsaturated group useful as a gw agent by reacting with (meth)acrylic acid (chloride), 2-isocyanate ethyl methacrylate, etc. It can be easily modified into terminal telechelic polymers, and its range of applications is extremely wide.

(Examples) Examples of the present invention are shown below, but these are given for illustrative purposes and are not intended to limit the scope of the present invention.
Further, in the following, parts and % represent parts by weight and % by weight, respectively.

Reference Example 1: 500 g of short methane was placed in a flask equipped with two dropping funnels, a pumper, a nitrogen introduction pipe, a thermometer, and a reflux condenser.
43 minutes while slowly blowing in nitrogen gas.
heated to ℃. there.

2.2°-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, hereinafter v-
A mixture consisting of 2.9 parts (denoted as 70), 200 parts of dioxane, and 246 parts of butyl acrylate were added dropwise over 7 hours.The temperature was maintained at 41 to 45°C during the dropwise addition, and the temperature was maintained at the same temperature for 2 hours after the completion of the dropwise addition. After stirring, the polymerization was completed, and the calculated polymerization rate was 100%. Subsequently, the pressure of this polymer [1] solution was reduced to 5 mmHH, and the solution was heated to 45 mmH.
By heating to ~50℃, residual dioxane and short methane are distilled off, and then reprecipitated with an ethanol/water system! ! After that, the obtained polymer [1] was dried at 45°C under reduced pressure.
] was purified. The properties of the polymer [1] after purification were as follows: number average molecular weight (Mn) 5100 (vapor pressure molecular weight measuring device (
vpo)), elemental analysis of camphor iodine content 4
．． 9%, and the number of terminal iodine functional groups (Fn(I)) was 2.0.

Reference Examples 2 to 6: Same as Reference Example 1 except that the polymerizable monomer, chain transfer agent (halogen compound), and polymerization initiator were used in the same amounts as shown in Table 1. Similarly, polymer [2]
~ [6] was obtained. The properties of the polymers [2] to [6] were as shown in Table 2.

Example 1 Polymer [1] 51w was placed in a flask equipped with a reflux condenser.
5, 200 parts of tetrahydrofuran, and 6.9 parts of a 35% aqueous sodium hydroxide solution were charged, and the mixture was reacted at 60° C. for 6 hours with stirring using a magnetic stirrer.
After the reaction, the polymer was extracted with toluene, washed once with a 1% aqueous sulfuric acid solution, then three times with ion-exchanged water, and finally dried at 60°C under reduced pressure to obtain a polymer [1°].
I got it.

The properties of the polymer [1°] are number average molecular weight (Mn) 510
0 (as measured by a vapor pressure molecular weight analyzer (VPO)), the iodine content by elemental analysis was 0.0%, and the number of terminal OHt m groups (Fn (OH)) was 2.0.
Furthermore, measurement of the acid value confirmed that almost no hydrolysis of the side chains of the polymer occurred.

Implementation f12-4゜In Example 1, the type and weight of the halogen-terminated telechelic polymer used for hydrolysis, the type and amount of the basic catalyst,
Polymers [2'] to [4'] were obtained by carrying out the same operation as in Example 1 except that the reaction temperature was changed as shown in Table 3. The properties of the polymers [2°] to [4'] were as shown in Table 4.

Example 5 51 parts of polymer [1], 3.7 parts of ethylene glycol, and 2 parts of tetrahydrofuran were placed in a flask equipped with a reflux condenser.
00 parts and 3.4 parts of a 35% aqueous sodium hydroxide solution were charged and reacted at 25° C. for 6 hours while stirring with a magnetic stirrer.

After the reaction, the polymer was extracted with toluene, washed once with a 1% aqueous sulfuric acid solution, then three times with ion-exchanged water, and finally dried at 60°C under reduced pressure to obtain a polymer [5''
] was obtained. The properties of the polymer (5') include a number average molecular weight (Mn) of 5100 (measured by a vapor pressure molecular weight analyzer (VPO)), an iodine content of 0.0% by elemental analysis,
Number of terminal OH functional groups (Fn (OH))1. It was called 9.

In addition, from the measurements made by VI, it was found that almost no hydrolysis of the side chains of the polymer occurred.1iiL! It was done.

Example 6.7 The amount of halogen-terminated telechelic polymer used in the substitution reaction, the weight of the diol compound, the seed layer and amount of the basic catalyst, and the reaction temperature are shown in Table 5. Implementation f! Perform the same operation as in step 5 to obtain 1 polymer [6゛] and [7°].
The properties of 6゛] and [7'] were as shown in Table 6.

Example 8 51 parts of polymer [1], 4.5 parts of N-methylethanolamine, and 200 parts of tetrahydrofuran were charged into a flask equipped with a reflux condenser, and reacted at 60°C for 6 hours while stirring with a magnetic cooler. I let it happen. After the reaction, excess N-methylethanolamine and tetrahydrofuran were removed with evaporated silane, reprecipitation was performed three times in an acetone/water system, and finally dried at 60°C under reduced pressure to obtain a polymer [8']. I got it. The properties of the polymer [8°] include a number average molecular weight (Mn) of 5200 (measured by vapor pressure molecular weight analyzer H (VPO)), a fiber content of 0.0% by elemental analysis, and a terminal 0H'iRM number (F
n(OH))1-9. Furthermore, measurement of the acid value confirmed that almost no hydrolysis of the side chains of the polymer occurred.

Example 9.10 Example 8 except that the MW and amount of the halogen-terminated telechelic polymer used in the substitution reaction, the type and amount of the hydroxyl group-containing amine compound, and the reaction temperature were as shown in Table 7. Perform the same operation as in 8 to obtain polymer [9'
], (10') were obtained. The polymer [9′],
The properties of (10') are probably as shown in Table 8.

Hell'1! 51 parts of polymer [1], 200 parts of tetrahydrofuran, 9.8 parts of sodium hydroxyacetate, 50 parts of ion exchange water, and 1.5 parts of tetra n-butylammonium bromide were placed in a flask equipped with an 11° reflux condenser. , 60'
After the reaction, the polymer was extracted with toluene, washed three times with ion-exchanged water, and finally dried at 60°C under reduced pressure. Coalescence (11') was obtained. The properties of the polymer [11''] are number average molecular weight (M n ) 5
300 (measured by vapor pressure molecular weight analyzer (VPO))
According to elemental analysis, the iodine content was 0.3% and the number of terminal OH functional groups (Fn (OH)) was 1.8.
From the measurement of the acid value, it was confirmed that there was almost no hydrolysis of the side chains of the polymer.

'p & example flow side, 13° implementation f! The same procedure as in Example 11 was performed, except that the type and amount of the halogen-terminated telechelic polymer used in the substitution reaction in 411, the Sa, amount, and reaction temperature of the hydroxyl group-containing carboxylate compound were as shown in Table 9. Polymers (12') and [13'] were obtained. U polymer [
12°] and [13°] were as shown in Table 10.

Example 14.15゜The same operations as in Example 1 were carried out except that the amount of 35% aqueous sodium hydroxide solution in Example 1 was as shown in Table 11, and polymers [14°], (15 ' ) was obtained. The properties of the polymers (14') and (15') were as shown in Table 11.

Example 16゜In Example 5, the amount of ethylene glycol added was 1.4
Polymer (16') was obtained by carrying out the same operation as in Example 5, except that The properties of the polymer [16°] are number average molecular weight (Mn) 7400 (measured by vapor pressure molecular weight analyzer (VPO)), iodine content according to elemental analysis *
0.9%, number of terminal OH functional groups (Fn (OH)) 1.6
That's what it was. In addition, the measurement of acid value showed that almost no hydrolysis of 11a in the polymer occurred.
tx was sent.

Example 17° A polymer [17°] was obtained in the same manner as in Example 8, except that the amount of N-methylethanolamine added was 1.8 parts. The properties of the polymer [17'] include a number average molecular weight (M n ) of 6200 (measured using a vapor pressure molecular weight analyzer (VPO)), an iodine content of 1.2% by elemental analysis, and a terminal oH1r functional group number (Fn (
OH)) 1.5. Furthermore, measurement of the acid value confirmed that almost no hydrolysis of the side chains of the polymer occurred.

Example 18° A polymer (18') was obtained by carrying out the same operation as in Example 11 except that the amount of sodium hydroxyacetate was changed to 3.9 parts. The properties of the polymer (18') include a number average molecular weight (Mn) of 5900 (measured using a vapor pressure molecular weight analyzer (VPO)), an iodine content of 1.7% by elemental analysis, and a terminal OH functional group number (Fn (OH ))1
．． It was called 3.

Comparison 9 Example 1゜9 In Example 1, the amount of butyl acrylate was 24 parts,
15 parts of dichloromethane instead of 500 parts of short methane
900 parts (polymerizable monomer/dichloromethane molar ratio is 0)
．． 01), the amount of V-70 was 144 parts (dichloromethane/
The molar ratio of V-70 is 400), the amount of dioxane is 300
A polymer for comparison and blue color [1] was obtained by carrying out the same operation as in Dream Example 1 except that The properties of the comparison and blue polymer [1] are as shown in Table 12.

Comparison 9 Example 2; In Example 1, instead of 500 parts of short methane, 1
．． 58,400 parts of 12-dibromododecane (molar ratio of polymerizable monomer/1.12-dibromododecane is 0.01),
■ The amount of -70 was 144 parts (the molar ratio of 1,12-dibromododecane/V-70 was 400), and the amount of dioxane was 30 parts.
Comparison 9 Polymer [2] was obtained by carrying out the same operation as in Example 1 except that the amount was 0 parts. Comparison and blue polymer [2]
The properties were as shown in Table 12.

Comparison and Examples 3゜In Example 1, the amount of short methane was 34゜3 parts (the molar ratio of polymerizable monomer/short methane was 15), and 500 parts of dioxane was initially added to the pot.
A comparison and blue polymer [3] was obtained in the same manner as above. M
The properties of Comparative 9 Polymer [3] were as shown in Table 12.

Comparison 9 Example 4゜9 In Example 1, the amount of jonidomethane was changed to 62,000 parts (
The molar ratio of polymerizable monomer/short methane is 0.0083
), 179 parts of ■-70 (short methane/V-7
Comparative Example 9 Polymer [4] was obtained by carrying out the same operation as in Example 9 except that the molar ratio of 0 was changed to 400). The properties of the polymer [4] used in the comparative book were as shown in Table 12.

Comparative Example 1゜The same operation as in Example 1 was carried out except that 1130 parts of Comparative Book Consideration Polymer (L) was used instead of 51 parts of Polymer (1) in Example 1, and the amount of tetrahydrofuran was changed to 2000 parts. A comparative polymer [1°] was obtained. The comparative polymer [
1°] has a number average molecular weight (Mn) of 118,000 (
(measured by GPC using a standard polystyrene calibration curve), iodine content 0.00% by elemental analysis, 0 terminals
H1r functional radical number (Fn (OH)) 0. It was called 5.

Comparative Example 2 - Comparison was carried out in the same manner as in Example 5, except that 51 parts of the polymer (1) was replaced with 231,020 parts of the comparison and blue polymer (231,020 parts) and the amount of tetrahydrofuran was 200 parts. Polymer [2゛] was obtained. The properties of the comparative polymer [2゛] were number average molecular weight (Mn > 110000 (
(Measured by GPC using a calibration curve with semi-polystyrene) Iodine content 0.00% by single element analysis, terminal O
The number of H functional groups (Fn (OH)) was 0.5.

Comparative Example 3゜*mSame operation as in Example 8 except that 970 parts of comparative polymer (3) was used instead of 51 parts of polymer (1) and the amount of tetrahydrofuran was changed to 1000 parts. A comparative polymer [3°] was obtained. The comparative polymer [3
'] properties are number average molecular weight (Mn) 100,000 (measured by GPC using a standard polystyrene calibration curve), iodine content *0.00% by elemental analysis, powder *OH
Number of functional groups (Fn (OH)) 0. It was 6.

Comparative Example 4 In Example 11, 970 parts of Comparative 9 Polymer (3) was used in place of 51 parts of Polymer (1), the amount of tetra-dolphuran was 1000 parts, and the amount of tetra-Ω-butylammonium bromide was A comparative polymer [4°] was obtained by carrying out the same operation as in Example 11 except that the polymer was changed to 15v5. The properties of the comparative polymer [4'] are number average molecular weight (Mn>10300
0 (I[*GPC using polystyrene calibration curve
(measured by), iodine content 0.02% by elemental analysis
, the number of terminal OHN n groups (Fn (OH)) was 0.5.

(Effects of the invention) The present invention itself provides polyurethane resin, polyester m
It is useful as a raw material for various coating resins such as fats, paints, adhesives, sealants, etc. It is also used as a precursor for telechelic polymers for use in balm, which have polymerizable unsaturated terminals such as acryloyl and methacryloyl groups. This method can easily and inexpensively produce a hydroxyl-terminated telechelic polymer that has a very wide range of applications and is extremely useful industrially.

By using the present invention, it is possible to use industrially advantageous radical polymerization from a wide range of polymerizable monomers, including polar polymerizable monomers such as acrylate esters and methacrylates, which has been difficult until now. It has become possible to easily and inexpensively produce telechelic polymers with terminal hydroxyl groups.

Table 1 Table 2 Measured by GPC using a calibration curve based on Enoki polystyrene.

Table 3 No. 4 JI! % Measured by GPC using a calibration curve based on Enoki polystyrene.

Table 7 Table 8 Measured by GPC using a standard polystyrene calibration curve.

Table 5 Table 6 Measured by GPC using a standard polystyrene calibration curve.

did.

Table 9 Table 10 did.

Table 1 1 Table 12 Measured by GPC using a standard polystyrene calibration curve.

Claims (1)

[Claims] 1. General formula (I) R^1X^1X^2 (I) (wherein R^1 is a divalent hydrocarbon group of C_1 to C_8,
X^1 and X^2 are each independently bromine or iodine. ) in the presence of a halogen compound (a) and a polymerization initiator (b), polymerize a polymerizable monomer (c) in an amount of 0.01 to 10 times the molar amount of the halogen compound (a). A method for producing a hydroxyl-terminated telechelic polymer, which comprises obtaining a halogen-terminated telechelic polymer, and then converting the terminal groups of the halogen-terminated telechelic polymer into hydroxyl groups using a substitution reaction. 2. The method according to claim 1, wherein the substitution reaction is hydrolysis in the presence of a basic catalyst (d). 3. The method according to claim 2, wherein the basic catalyst (d) is a compound containing an alkali metal. 4. The substitution reaction is carried out with a halogen-terminated telechelic polymer in the presence of a basic catalyst (e) and the general formula (II) HOR^2OH (II) (wherein R^1 is C_1~ which may have a substituent) C_1
It is a divalent hydrocarbon group of _8. ) and/or general formula (III) HO-(R^2-O)_n-H(III) (wherein, R^2 is C_1 to C_1 which may have a substituent
It is a divalent hydrocarbon group of _8, and n is an integer of 1 to 1000. ) The method according to claim 1, wherein the diol compound (f) is represented by: 5. The method according to claim 4, wherein the basic catalyst (e) is a compound containing an alkali metal. 6. Substitution reaction with halogen-terminated telechelic polymer,
General formula (IV) R^4NHR^5OH (IV) (In the formula, R^4 is hydrogen or an alkyl group of C_1 to C_1_8, and R^5 is a divalent hydrocarbon group of C_1 to C_1_8.) The method according to claim 1, which is a reaction with a hydroxyl group-containing amine compound (g). 7. The method according to claim 6, wherein the hydroxyl group-containing amine compound (g) is a secondary amine compound. 8. Substitution reaction with halogen-terminated telechelic polymer,
Hydroxyl group-containing carboxylate compound (h ) The method according to claim 1, wherein the method is a reaction with 9. The polymerizable monomer (c) is an acrylic ester and/or
or methacrylic number ester. 10. The method according to claim 1, wherein the halogen compound (a) is an iodine compound.