JPH04149208A - Production of telechelic polymer terminated with amino group - Google Patents

Abstract

PURPOSE:To easily obtain at low cost the title polymer to be used as a polyamide resin by polymerizing a polymerizable monomer in the presence of a specific halogen compound and polymerization initiator into a halogen-terminated telechelic polymer followed by converting the terminal group to amino group. CONSTITUTION:In the presence of a halogen compound of formula I (R<1> is 1-8C divalent hydrocarbon; X<1> and X<2> are each Br or I) (e.g. diiodomethane) and a polymerization initiator [e.g. 2,2'-azobis(4-methoxy-2,4-divaleronitrile)], 0.01-10 molar times (based on this halogen compound) of polymerizable monomer (e.g. butyl acrylate) is polymerized into a halogen-terminated telechelic polymer. Then the terminal group(s) of this polymer is converted to amino group(s) by reaction of an amine compound of formula II (R<1> and R<2> are each H, 1-18C alkyl, phenyl, etc.) (e.g. ammonia) taking advantage of substitution reaction, thus obtaining the objective polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION FIELD OF APPLICATION ON CAP 1) The present invention III As a polymer which itself has terminal reactive groups, polyamide 1! It is very useful as a raw material for fats, polyurea, hardened paints, adhesives, sealants, etc., as well as various terminal telechelic polymers such as vinyl-based (meth)acryloyl, diboxyl, oxazolinyl, and aziridinyl groups. The present invention relates to a method for producing an amino group-terminated telechelic polymer that can be converted into a polymer.

(U point to be solved by the prior art and the present invention) Telechelic polymers ideally have one function f:i& at each end of the polymer, so polyurethane mu, epoxy SL etc. A variety of! ! ! When used for riverside applications, it is ensured that there are no unreacted substances that impair the physical properties of the material.
ilf: Incorporated into the structure In addition, the distance between reaction points (between crosslinking points) is constant and a uniform structure is created, so the characteristics of the telechelic polymer itself are fully utilized! ! It has the great advantage of being able to be inserted, so 1 of each! ! It is very useful as a raw material for tMff, law materials, adhesives, sealants, etc. Among them, amino group-terminated telechelic polymers include polyamide 1118,
It is also very useful industrially as an M material for curing agents such as polyurea resins and Nipoxy 11i+a. the current,
Polyether-based and polyester-based polymers are commonly used as telechelic polymers that are used industrially, but they still have drawbacks such as poor weather resistance and water resistance. On the other hand, it is not difficult to industrially synthesize vinyl-based telechelic polymers, and some polybutadiene telechelic polymers are known, but these do not fully overcome the drawbacks of polyester-based telechelic polymers. WL 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 M and methacrylic esters The traditional W method for making telekeric polymers is currently not available! The current situation is that it has not been established.

Halogen atoms such as chlorine and chlorine are highly reactive blind groups, and a halogen-terminated telechelic polymer having such halogen atoms at both ends of the polymer is used as an intermediate to form various amines with terminal halogen atoms. By utilizing a substitution reaction with a compound, it is possible to easily synthesize a telechelic polymer having an amino group at the end.

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

A typical example is the polymerization of ethylene using carbon tetrachloride. The polymer customer C1-(cHt-(:Ht)--CCIs (n=1
~10), and has halogen atoms at both ends, but the number of terminal halogen atoms is l
! , 311 are heterogeneous, and even if III reactions are performed with various amine compounds, some react with only 1ffi of the three halogen atoms at one end, some react with 21ml, and some react with 5fil. The reaction (wheat structure) becomes non-uniform, making it impossible to synthesize an ideal telechelic polymer.

Purpose version of the present invention As a polymer that itself has a terminal reactive group, it is very useful as a material for polyamide resins, polyurea resins, curing agents, crosslinking agents, law materials, IS agents, sealing materials, etc. By using a halogen-terminated telechelic polymer synthesized by a telofluorization reaction as an intermediate, and converting the terminal halogen atom into an amino group using a substitution reaction, The object of the present invention is to provide an easy and inexpensive manufacturing method.

(Moves 1 and 2 and actions to solve the problem) Honkabuto l1
A halogen-terminated telechelic polymer obtained by polymerizing a polymerizable monomer in the presence of a compound containing two halogen atoms consisting of JK element and/or iodine in the 11 molecules and a polymerization initiator. By performing a substitution reaction with a highly reactive halogen atom at the terminal with various amine compounds, even when the polymerizable monomer contains polar monomers such as acrylic esters and methacrylic esters, the amino group terminal The present invention was achieved by discovering that telechelic polymers can be easily and inexpensively synthesized.

That is, the present invention provides a halogen compound represented by the general formula (1) % formula % (in the formula, R is Ct to C. 2ai carbide sailor LXXi are each independently a pure sum or iodine) (a), and in the presence of a polymerization initiator (b), 0.01 to 10% relative to the halogen compound (a).
An amino group characterized by polymerizing twice the molar amount of the polymerizable main polymer (c) to obtain a halogen-terminated telechelic polymer, and then converting the halogen-terminated telechelic polymer into an amino group using a substitution reaction. This paper relates to the Sl method for terminal telechelic polymers.

As the halogen compound (a) represented by the general formula (1) used in the present invention, for example, dibromomethane, 1.1
-dibromoethane, 1.2-dibromoethane, 1.2
-dibromopropane, 1.3'' dibromopropane, 1
．． 3-dibromobutane, 1゜4-dibromobutane, l
, 5-dibromopentane, 1,6-dibromohexane,
l, 7-dibromohebutane, l, 8-dibromooctane, 1,2-dibromoethylene, 2,3-dibromopropene, short methane, 1,1-short ethane, 1,2-short ethane, 1,2- Examples include short ethylene, bromoiodomethane, 1-bromo-2-iodoethane, etc. One or 21 of these
! Mixtures of one or more can be used.

Among these, short methane, l, 1-short ethane, 1. 2-Short ethane, 1.2-
Iodine compounds such as short ethylene have a large chain transfer constant, facilitate telomerization, and have a high number of terminal halogen functional groups (Fn (1)) in the resulting telechelic polymer (approaching 2.0), so they are highly preferred. .

In addition, I
For example, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, w12-ethylhexyl acrylic, dodecyl acrylate, stearyl acrylate, 122-hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, acrylic 1a2-N,N-dimethylaminoethyl and its 4 Sl 24, acrylic esters such as monoacrylic shark ester of polyethylene oxide jJ: Methacrylic 1 Methyl methacrylate, nityl methacrylate, butyl methacrylate, methacrylic shark cyclohexyl, methacrylic M2- Ethylhexyl, dodecyl methacrylate, stearyl methacrylate, methacrylic 122-hydroxyethyl, methacrylic shark hydroxypropyl, glycidyl methacrylate, methacrylic M2
-N,N-dimethylaminoethyl and its quaternary filling, methacrylic esters such as monomethacrylic ester of polyethylene oxide; maleic acid, maleic anhydride, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, fumaric acid Monofulkyl esters and dialkyl esters of: styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, styrene derivatives such as styrene sulfonic acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide,
Maleimide derivatives such as dodecylmaleimide, ste7lylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing polymerizable monomers such as 7crylonitrile and methacrylonitrile; amide group-containing polymerizable monomers such as acrylamide and methacrylamide vinyl esters such as vinyl acetate, vinyl propionate, vinyl piperate, and vinyl benzoate; dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, furyl alcohol, etc. It can be used alone or in a mixture of two or more.

Among these, when acrylic esters and methacrylic esters are used, telechelic polymers with better 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 acrylic 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 carmer (e) is 0 with respect to the halogen compound (a).
．． Must be used in an amount of 0.1 to 10 times the molar amount,
If the amount used is less than 0.01 times the mole, the progress of polymerization will be hindered and the number of polymerizable groups will decrease.

Furthermore, if the amount exceeds 10 times the molar amount, Mtli transfer will not occur sufficiently, and the number of terminal halogen groups in the resulting polymer will be limited. Preferably, it is in the range of 1 to 5 times the mole of O.

The polymerization initiator (b) can be used without any restriction as long as it has been conventionally used for radical polymerization of polymerizable monomers. The amount used can vary widely depending on the properties of the obtained telechelic polymer, but the molar ratio of halogen compound (a)/polymerization initiator (b) is 50 to 5.
If the 0wi 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, and if it exceeds 500, the number of terminal halogen functional groups will decrease. The progress of polymerization may be hindered and the amount of polymerization may decrease.

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 undesirable to use a large amount of a solvent with a large transfer constant, for example a chain transfer constant of 1 x 10°4 or more, as this will reduce the number of terminal halogen functional groups in the resulting polymer. The temperature ranges from 20 to 120℃, preferably from 20 to 120℃.
The temperature is more preferably 80°C, and even when bimolecular termination occurs, the formation of terminal double bonds in the polymer due to disproportionation termination is avoided, and the number of terminal halogen functional groups is not reduced due to recombination termination. In order to efficiently introduce halogen atoms into both ends, the temperature is particularly preferably 20 to 50°C.

Specific examples of the polymerization initiator (b) include, for example, 2°2°-
7zobisisobutyronitrile, 2,2゜azobis(2,
4-dimethylvaleronitrile), 2.2°-7zobis(
4-methoxy-2,4-dimethylvaleronitrile), 4
, 4°-azobis(4-cyanopentane R), etc.; Oxidation? 1-based initiators; redox-based initiators such as Fe"/Kodama peroxide, hydrogen peroxide/7-Scorbin shark, and benzoyl oxide/dimethylaniline, etc. Used alone or in a mixture of 211 or more of these. However, since it is more preferable to conduct the polymerization at a low temperature, among these initiators, 2,2°-azobis(4-methoxy-2°4-dimethylvaleronitrile), isobutyryl peroxide, tert-butyl More preferred are pivaloyl peroxide, redox initiators, and the like.

In the method of the present invention, the terminal halogen atom of the halogen-terminated telechelic polymer is converted into an amino group using a substitution reaction. Although the type of Nl+ reaction is not particularly limited, substitution reactions with various amine compounds are advantageous in terms of reaction efficiency and resistance to scission of the main chain or side chain of the telechelic polymer.

The substitution reaction will be described in detail below.

General formula (Ill) RINHR used in the substitution reaction of a halogen-terminated telechelic polymer with one terminal halogen
(11) (In the formula, R1 and Rt are each independently hydrogen or an alkyl or alkenyl group of 01 to 010 which may have an Ill group, or a phenyl group which may have an Ill group.) As the amine compound (d) represented by I
Ammonia, methylamine, ethylamine, n-propylamine, n-butylamine, n-hexylamine,
n-octylamine, 5ec-octylamine, ter
t-octylamine, n-decylamine, n-dodecylamine, n-stearylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, dihexylamine, di-n-octylamine, di-n-decyl 7 Mine, N-methyl-n-butyl7Min, N
-Methyl-n-hexylamine, aniline, N-methylaniline, N-nitylaniline, n-butylaniline,
Ethanolamine, N-methylethanolamine, etc. can be used as IN or a mixture of two or more thereof.

The terminal amino group of the amino group-terminated telechelic polymer synthesized by this production method is more widely used than the primary or secondary amino group that has an active hydrogen that can react with other reactive groups. As the amine compound (d), a 1 ml amine compound is preferable, and ammonia is more preferable, since it is more useful.

Amine combination with terminal halogen atom of halogen-terminated telechelic polymer? The molar ratio of m(d) during the substitution reaction may be as long as the amine compound (d) is equimolar or more to the polymer-terminated halogen plate, but if the amine compound (d) is ammonia or a 1m amine compound. ,ffHI
The 1m amino group or secondary amino group at the end of the polymer generated by JE reaction further undergoes a substitution reaction with a halogen atom at the end of the polymer to increase the molecular weight of the resulting polymer (secondary or tertiaryization of the primary or 211 amino group) In order to avoid this, it is preferable that the amine compound ((1) be present in excess with respect to the terminal halogen atoms of the polymer.

Specifically, amine compound for polymer Song end halogen plate? The amount of I(d) added is preferably 3 times the molar amount or more,
More preferably, the amount is 10 times the molar amount or more.

There is no particular restriction on the solvent used in the 3111 reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and the amine compound (d), but the halogen-terminated telechelic polymer and the amine compound (d) are mixed in a uniform or nearly uniform state during the reaction. The one that can be made into n is good, and the isomers include methanol,
Alcohols such as ethanol and isopropanol, and highly polar substances such as acetone, tetrahydrofuran, and dioxane are preferred).

Further, additives such as phlegm may be freely used in the substitution reaction.

The temperature during the substitution reaction between the terminal halogen 2 molecules of the halogen-terminated telechelic polymer and the amine compound (d) can be arbitrarily selected, but is preferably 50°C to 150"C, and 50°C to 100"C.
C. is more preferred.

General formula (m) R”NER4 used for whfLz with terminal halogen button of halogen-terminated telechelic polymer
N (R')Rt (m)(R", Rt and R81=
C which may each independently have a hydrogen or ll substituent
I-C+ s is an alkyl or alkylene chain or a phenyl group which may have a substituent, and R1 is 01-
It is a divalent hydrocarbon group of CII. ) as the amine compound (e) 1 ethylenediamine, N,
N-dimethylethylenediamine, tetramethylenediamine, N.

Examples include N-dimethyltetramethylenediamine, hexamethylenediamine, N,N-hexamethylenediamine, octamethylenediamine, N,N-octamethylenediamine, dodecylmethylenediamine, octadecylmethylenediamine, diethylenetriamine, etc.
These can be used alone or in a mixture of two or more.

The terminal amino group of the amino group-terminated telechelic polymer synthesized by this production method. It is preferable to use a primary or secondary amine group having an active hydrogen that can react with other reactive groups. As the amine compound (e), it is preferable to use ethylenediamine, which has two active hydrogen atoms and produces a highly reactive primary amine after reaction with a halogen-terminated telechelic polymer.

The molar ratio of the terminal halogen atom of the halogen-terminated telechelic polymer and the amine compound (e) during the substitution reaction may be as long as the amine compound (e) is equimolar or more to the terminal halogen atom of the polymer, but if the amine compound < e > has two or more active hydrogen atoms on the iiE element of the compound, the amino group having the active hydrogen at the end of the polymer generated by the substitution reaction is further bonded to the halogen atom at the end of the polymer.
The molecular weight of the produced polymer is increased by the l-substitution reaction (Production 1
In order to avoid 2i1 or tertiaryization of secondary or secondary amino groups, it is preferable that the amine compound (e) is present in excess with respect to the halogen atom. The amount of e) added is preferably at least 3 times the molar amount, more preferably at least 10 times the molar amount.

There is no particular restriction on the solvent used in the substitution reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and the amine compound (e), but the solvent used in the substitution reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and the amine compound m<e> is uniform or nearly uniform during the reaction. Preferable examples include alcohols such as methanol, ethanol and isopropanol, and highly polar substances such as acetone, tetrahydrofuran and dioxane.

Further, additives such as phlegm may be freely used in the substitution reaction.

The temperature during the substitution reaction between the terminal halogen atom of the halogen-terminated telechelic polymer and the amine compound (e) can be arbitrarily selected, but is preferably 50°C to 150°C, and 50°C to 80°C.
is even more preferable.

Ideally, the number of terminal functional groups in a telekeric polymer is 2.0 in one molecule, but even if the number of +Nu groups is less than 2.0, industrial usefulness is not lost, and the average number of terminal functional groups in one molecule is If the number of hydroxyl functional groups is greater than about 1°8, it is possible to exhibit physical properties almost equivalent to ideal ones.

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 amino group-terminated telechelic polymer of the present invention can be used as a raw material for polyamides, polyureas, curing agents, crosslinking agents, legal materials, adhesives, sealants, etc. by utilizing the reactivity of its terminal amino groups. In addition to being used for various purposes, it can also be modified into various terminal telechelic polymers such as vinyl 1&, (meth)7 chloroyl, epoxy, oxazolinyl, and aziridinyl groups, and its range of applications is extremely wide. be.

(Effect of the invention) Zero-starting Q-mountain itself polyamide resin, polyurea vBH
It is useful as a raw material for curing agents such as Nato, epoxy TJILFF, various crosslinking agents, legal materials, adhesives, sealing materials, etc., and is also useful as a raw material for vinyl T&S (meth)acryloyl group, epoxy group, oxazolinyl, aziridinyl group, etc. This is a two-way method that can easily and inexpensively produce amino group-terminated telechelic polymers that can be used as nu-terminated telechelic polymers, have a very wide range of applications, and are extremely useful industrially. Book! ! By using this method, industrially advantageous radical polymerization can be used to convert broad polymerizable monomers, including polar polymerizable monomers such as acrylic esters and methacrylic esters, which has been difficult until now. It has become possible to easily and inexpensively HM a telechelic polymer having terminal amino groups.

(Example) Below, the English [Q of book qQ is shown, but these are listed for illustrative purposes. ! It does not limit clarity,
In addition, in the following, L% represents weight percentage.

Small example 1゜Two dropping funnels, stirring ILi! Introducing short methane 5005 into a 4-bottle flask with a detonator tube meter and an FH cooler placed on the side. Slowly 1! It was heated to 43°C while boiling in purple gas. There, 2,2'-azobis(4-methoxy-2,4-dimethy9valeronitrile)
(V-70, manufactured by Wako Pure Chemical Industries, hereinafter referred to as v-70)2.
A mixture of 200 parts of 91L dioxane and 246 parts of butyl acrylate was added dropwise over 7 hours.The temperature was maintained at 41-45°C during the dropwise addition, and after the completion of the dropwise addition, the temperature was maintained at 41-45°C.
After stirring at the same temperature for a period of time, the polymerization was completed and the polymer [1
] was obtained. The polymerization vehicle calculated from the solid content concentration at this time was 100%. In conclusion, this polymer [
1] solution was depressurized to 5 mmHH and heated to 45-50"C to distill off residual dioxane and short methane, and then reprecipitated with ethanol/water system, then heated to 45 °C under reduced pressure.
The obtained polymer [1] was purified by drying. Properties of the polymer [1] of 糟Xi
n) 5100 (as measured by a vapor pressure molecular weight analyzer (VPO)), an iodine concentration of 4.9% by elemental analysis, and a terminal functional group number (Fn(I)) of 2.0.

9 Examples 2 to 5゜9 Example fR1 except that the types and amounts of the polymerizable monomer, G1Sm agent (halogenated compound?&l), and polymerization initiator were as shown in Table 1 in i. Polymers [2] to [5] were obtained in the same manner as in Example 1. The properties of the polymers [2] to [5] were as shown in Table 2.

Implementation 51 Charge 51 parts of polymer (1), 200 parts of tetrahydrofuran, and 6.1 parts of 28% ammonia aqueous solution into an autoclave.
The reaction was carried out at ℃ for 1 hour with stirring. After the reaction, remove the solvent and excess ammonia using an evaporator, and then re-precipitate twice using an acetone/HxO system.
A polymer [1”] was obtained by drying under reduced pressure at 80°C. The properties of the polymer [1°] were number average molecular weight (Mn)
51゜0(a)it pressure molecular weight measuring device f (TPO)
(measured by), 0.0% by elemental analysis,
Terminal 7 min if f: l number (Fn (amine))2.
0 (measured by potentiometric titration with p-toluenesulfone MrPH solution in dioxane/acetic acid M mixed solvent).
It was found that almost no single chain hydrolysis occurred.

Example 2 In Example 1, place! Polymer (2) 611L of the halogen-terminated telechelic polymer to be used for one scale reaction 0.1NL of a 40% methanol solution of methylamine
A polymer [2°] was obtained by carrying out the same operation as in Example 1 except that the reaction time was changed to 3 cycles.

The properties of the polymer [2°] are number average molecular weight (Mn) 620
00 (GPC using a calibration curve with II quasi-polystyrene
(measured by), JE elemental collection 0.0% by elemental analysis,
The number of terminal amine functional groups (Fn (amine)) was 1.8 (measured by potentiometric titration with a 12 solution of p-)luenesulfonic acid and vinegar in a dioxane/vinegar Wl mixed solvent). Also, the acid value was measured. It was found that almost no hydrolysis of the side plate of the polymer occurred.

Actual) I inverted 3 In a flask equipped with a reflux condenser, 99 parts of polymer [3], n-hexylamine lo, 11 L dioxane 20
Charge 0B and react at 60°C while stirring with a magnetic stirrer. After JE reaction, after removing the solvent and excess n-hexylamine with an evaporator, reprecipitation was performed twice with acetone/B hot 0 system, and then 80%
A polymer [1°] was obtained by drying under reduced pressure at °C.

The properties of the polymer [l°] are number average molecular weight (Mn) 1
0000 (measured by vapor pressure molecular weight analyzer (VPO)), 0.1% iodine concentration by elemental analysis, number of terminal amine functional groups (Fn (amine)) 1.8 (dioxane/
p-toluenesulfone in vinegar 12 mixture fs viper
In addition, MfE measurements confirmed that almost no hydrolysis of the polymer chains occurred.

Examples 4 to 8 The type and amount of the halogen armament telechelic polymer used in the fil conversion reaction in Example 3, the type of amine compound, and! And reaction temperature, reaction time 3rd! The same operation as in Example 3 was carried out except for the consistency shown in I, to obtain tX1 polymers [4°] to [8°].

The properties of 1111 coalescence [4"] to [8°] were as shown in Table 4.

Example 9 In Example 1,! Same as Example 1 except that the amount of 28% ammonia aqueous solution used in the sandwich reaction was 1.5 parts!
IIW! The following operations were performed to obtain a polymer [9°]. The properties of the polymer [9°] are number average molecular weight (Mn) 6500
(Vapor pressure molecular weight measurement!! Measured by i&(VPO))
, 0.2% iodine concentration by elemental analysis, terminal amine i
The number of r functional groups (Fn (amine)) was 1.9 (measured by potentiometric titration with p-1-luenesulfone shark acetic acid solution in a dioxane/acetic acid mixed solvent).
Furthermore, measurement of the acid value revealed that almost no hydrolysis of the g1 chain of the polymer occurred.

Example 10 A polymer [10°] was obtained in the same manner as in IN Example 6, except that the amount of ethylenediamine used in the III reaction in Example 6 was changed to 2.0 g.

The properties of the polymer [10°] are number average molecular weight (M-H)
780'O (M atmospheric pressure molecule jlfi constant device E (VPO
) 1 element analysis is 0.1%
, the number of terminal amine functional groups (Fn (amine)) was 1°9 (measured by potentiometric titration with a dioxane/vinegar [P-] luenesulfonic acid acetic acid solution in a mixed solvent), and from the measurement of mar. It was determined that a = almost no hydrolysis of the 11 chains of the polymer occurred.

Comparative Reference Example 1゜9 In Example 1, the amount of butyl acrylate was 24 parts,
1 dichloromethane instead of 500 gL of short methane
5,900 parts (the molar ratio of polymerizable monomer/dichloromethane is 0.01), the amount of ■-70 is 144iE (the molar ratio of dichloromethane/V-70 is 400), and the amount of dioxane is
006! Perform the same operation as in Reference Example 1 except that the ratio I
2 Firefly reference polymer [1] was obtained.・The comparative reference polymer (
The properties of 1) were as shown in Section 5H.

Comparison 9 Consider fF12° in mold can 1 instead of 500 parts of short methane.
1. 58,400 parts of 12-dibromododecane (polymerizable carmer/L12-dibromododecane, FL4+: 0.
01), the amount of V-70 was 144 parts (the molar ratio of 1,12-dibromododecane/V-)0 was 400), and the amount of dioxane was 300 parts, but the same operation as in Reference Example 1 was carried out for comparison. A reference polymer [2] was obtained. ! The properties of Comparison I Comparison 9 Polymer [2] were as shown in Table 5.

Ratio f22 Consideration 3゜9 In Example 1, the amount of short methane is 34゜3i! (
The molar ratio of polymerizable carmer/short methane is 15),
9 Example 1 except that dioxane SOO* was added to the pot at the beginning
The same operation as above was carried out to obtain a comparative reference polymer [3].
The properties of the comparative reference polymer [3] were as shown in Table 5.

Comparison 9 Thoughts 4゜Small In Example 1, the amount of short methane was 62,000 parts (
Molar ratio of polymerizable monomer/short methane! :0.008
3), the amount of V-70 was 179 parts (short methane/V-
A comparative reference polymer [4] was obtained by carrying out the same operation as in Example 9 except that the molar ratio was 400). ! The properties of the I ratio I2 polymer [4] were as shown in Table 5.

Comparative Example 1゜In Example 1, instead of 51 parts of polymer (1), the ratio ff
A comparative polymer [1°] was obtained by carrying out the same operation as in Example 1, except that 1130 parts of TFT heavy polymer were used and the amount of tetrahydrofuran was changed to 2000 parts. ! [Comparative polymer]
1°] has a number average molecular weight (Mn) of 118,000 (
(Measured by GPC using a calibration curve with W quasi-polystyrene), salt content of 0.00% by elemental analysis, terminal amine content Wi&l! (Fn(amine)) 0.5 (measured by potential measurement with P-toluenesulfonic acid solution in dioxane/vinegar 12ffi solvent) 1) Using 1020 g of Comparative P Commercial Polymer (2) instead of 51 parts and changing the amount of dioxane to 2000 parts, the same operation as Fu Nfl 6 was performed to obtain %z Comparative Polymer [2゛] .

The properties of the comparative polymer [2”] are number average molecular weight (Mn) 1
10,000 (measured by GPC using a calibration curve with It quasi-polystyrene), bromine-containing go by elemental analysis,
oo%, number of terminal amine functional groups (Fn (amine)) 0.5
(Measured by potentiometric titration with a solution of p-)luenesulfone in a mixed solvent of dioxane/acetic acid).

Comparative Example 3 In Example 7, 970 parts of comparative reference polymer (3) was used instead of 51 parts of polymer (1), and the amount of dioxane was changed to 1
Except for 000 copies, X*N7 and p! Comparative polymer [3'] was obtained by performing the procedure IIl.

The properties of the comparative polymer [3°] are number average molecular weight (Mn) 1
00000 (measured by GPC using a calibration curve with 11 quasi-polystyrene), Iodine blue gold yield by elemental analysis 0
．． 00%, terminal amine Wc group t(Fn(amine)) 0.
6 (measured by potentiometric titration with an acetate shark solution of P-)luenesulfone 12 in a mixed solvent of dioxane/acetic acid M).

Table 1 Table 2 * Measured by GPC using a standard polystyrene calibration curve.

Table 3 Table 4 Calibration using standard polystyrene Calibration was carried out by GPC using GPC.

Table 5 * Measured by GPC using 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 an amino group-terminated telechelic polymer, which comprises obtaining a halogen-terminated telechelic polymer, and then converting the terminal group of the halogen-terminated telechelic polymer into an amino group using a substitution reaction. 2. Substitution reaction with halogen-terminated telechelic polymer,
General formula (II) R^1NHR^2 (II) (In the formula, R^1 and R^2 are each independently hydrogen, an alkyl or alkenyl group of C_1 to C_1_8 which may have a substituent, or a substituted Claim 1 is a reaction with an amine compound (d) represented by (a phenyl group which may have a group)
Manufacturing method described. 3. The method according to claim 2, wherein the amine compound (d) is ammonia. 4. The method according to claim 2, wherein the amine compound (d) is a primary amine compound. 5. Substitution reaction with halogen-terminated telechelic polymer,
General formula (III) R^3NHR^4N (R^5) R^6 (III) (R^3
, R^5 and R^6 are each independently hydrogen, an alkyl or alkylene group of C_1 to C_1_8 which may have a substituent, or a phenyl group which may have a substituent, and R^4 is It is a divalent hydrocarbon group of C_1 to C_1_8. 2. The method according to claim 1, wherein the reaction is with an amine compound (e) represented by: 6. The method according to claim 4, wherein the amine compound (e) is ethylenediamine. 7. Polymerizable monomer (c) is acrylic ester and/or
or methacrylic acid ester. 8. The method according to claim 1, wherein the halogen compound (a) is an iodine compound.