JPS60229913A - Polyalkenyl ether block copolymer - Google Patents

Abstract

PURPOSE:The titled copolymer usable in new fields because of solubility and chemical properties different from those of ordinary diblock copolymers, having a specific structure, narrow molecular weight distribution, consisting of three or more kinds of chains. CONSTITUTION:For example, an alkenyl ether such as methyl vinyl ether, etc. is polymerized by the use of a mixture of HI and I2 as an initiator. Further, after the polymerization is over, another kind of alkenyl ether is added to the polymerization system, and polymerization is carried out, to give the desired copolymer having a structure shown by the formula (R<1> and R<3> are H, or CH3; R<2> and R<4> are different alkyls; n1 and n2 are >=2 integer), molecular weight distribution prescribed shown by Mw/Mn of <=1.3, consisting of three kinds of chains.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyalkenyl ether block copolymers.

Alkenyl ethers polymerize only through cationic polymerization, but
In the case of cationic polymerization, migration and termination reactions are generally likely to occur, so living growth does not occur, and polymers with a narrow molecular weight distribution and block copolymers are difficult to form.

One of the present inventors and P. Kennedy synthesized a polyvinyl ether triblock copolymer of methyl vinyl ether-isobutyl vinyl ether-methyl vinyl ether using a method called the quasi living cationic polymerization method. ( , T., Maaromo
l Sci, Chem, A/I/317/
-13i3('tλ-tr3)) L, while Mw
/Mn was 1, ≠ or more, and a narrow distribution was not obtained.

[
Proceedings of the Society of Polymer Science and Technology.

3ko, tt'y, itt, iyo, /443ta, ldahiro3 (/913)).

By the way, the molecular weight distribution is narrow (MY/Mn </, J)
A block copolymer consisting of three or more types of chains has a large physical property difference from a diblock copolymer (indicating anyl ether unit).The A%B, C... components of the block copolymer are all My. /Mn </, My/Mn<83 of the block copolymer (ABC...) as a whole
It is.

Here, Mw /d is the weight average molecular weight, Mn is the number average molecular weight, and the MY/Mn ratio is determined by G'PC (polystyrene calculation).

Column: Showa Denko polystyrene gel 1ro2゜ltθ
3. ArO Hiromu; Inner diameter tm, length zookaku (manufactured by JASCO Corporation)
TRIROTAB' Chromatograph) (1) and (
Since the initiator in 2) is a co-functional initiator, the resulting polymer is a block polyalkenyl and ether copolymer of the BAB type (A%B,... are different types of polyesters). It can also be an alkenyl ether unit.

When using the initiators (1) and (2), CHR'=CH-0-(CH,)n-〇-crr=cy
In p' (i), R'' R6, R?, R11 represent -H or -CH8'ft, and n represents a natural entity.Specific compounds include (R/+≠-divinyloxyptane (R'= R'=H)
01) /, Dervis (l-iodoethoxy)butane (
R = R'' = H).

When using the initiator (2), the ratio of (1) to HI is λ:
/-/: 10 is desirable.

When using the initiators (1) and (2), the amount of
) or (11) is preferably j near to /:l.

Initiator (1), Hl and 1. (II) and (2) may be mixed in advance or added separately at the start of polymerization. When initiator (3) is used, since it is a monofunctional initiator, it can be produced in either ABC type or ABA type depending on the type of monomer used. Furthermore, functional groups and double bond groups can be introduced at the terminals, making it possible to synthesize novel macromers. When using the initiator (3), HI and I.

The ratio is preferably 1:2 to 0:/.

The next one is the nanatsuma, but generally CHR” =
CH(OR'') and the alkyl group may be branched or linear, and may be substituted with a hetero group.

As a specific example, R・RIO Methyl vinyl ether HCHH I Chill ECCHa Isopropyl I HCH (CH,).

n-Butyl H(CH鵞)scHs Isobutyl #, HCH, CH(CH,) meaning cyclohexyl z H(◇ n-hexadecyl I H(CH,),, CH.

Coke tetraloethyl #)I CMiiCH4CjR・,
RIG Methyl propenyl ether CH, CH.

Ethyl 5 CH, C, H.

Isopropyl I CHa CH(CMg)*n-butyl #CHs(CH,), CH.

Isobutyl z CHj CHICH(CHa)戈-
Examples include hexadecyl' CHs (CHa)twcHmcochloroethyl #CH, CH, CH, Cj.

Polymerization initially converts a specific alkenyl ether into (1), (
2)% (a) The method is to carry out polymerization using at least seven initiators, and when the polymerization is completed, to add another type of alkenyl ether, which can be repeated successively thereafter.

The generated polymer is 100HR"-C'H (OR Lee-) (-caR"-aH(
oR') It has an n-fold structure, and the molecular weight distribution is MY/Mn

That is, any amount may be used as long as the degree of polymerization of one polyalkenyl ether unit is λ or more.

You can stop the polymerization in any way you like at the end of the final polymerization, but (
υ, when using the initiator tube of (2), when ammonia, primary amine, secondary amine, alcohol, thiol, or cyanide compound is used, both ends are -NH,, -NHFt,
-HR, -OR, -8R, -CM.

(R here represents an alkyl group) When using an initiator of %(3), a functional group as shown above can be inserted at one end, and when a strong base such as tBuOK is used, a double bond can be introduced. It is also possible.

The thus obtained block polyalkenyl ether copolymer composed of three or more types of chains with a narrow molecular weight distribution. They have the same composition but different chemical properties such as solubility.

Therefore, it is expected that it will be used in fields where diblock polyalkenyl ether copolymers have not been used. For example, it will be possible to use a reaction field using this polymer to cause a new chemical reaction (hydrophobic reaction in a hydrophilic field, etc.).

This polymer is also used as a surfactant. In this case, it is desirable to use it in applications that take advantage of the chemical properties of three or more types of chains, such as low-foaming detergents, emulsifying and dispersing agents, and the like.

When the initiators (1) and (2) are used, this polymer can be used to obtain telechelic polymers, and when chain-extended, it can be used in antithrombotic materials, thermoplastic nidistomers, artificial leather, etc.

When the initiator (3) is used, a block copolymer consisting of three or more types of chains of ABC type (M, B, and C represent different types of polyalkenyl ether units) is produced. Various types of poly(i-) with different chemical properties can be produced and used for various purposes.

When carrying out the polymerization reaction, it may be carried out in bulk, but 1. Examples of the usual solvents include aliphatic hydrocarbons such as n-hexane and cyclohexane, aromatic hydrogen chloride such as toluene, and carbon tetrachloride.

It is preferable to use Yoka Genka Disaster Hydrogen, etc.

The charging ratio of solvent and monomer is usually preferably /:/-100:l.

The polymerization temperature is preferably room temperature or lower, particularly preferably -C or lower.

The ratio of each monomer to initiator is determined depending on the length of the chain produced.

This will be explained below using examples.

Example 1 Ailm triblock copolymer, poly(MVI-bo
vB-b-Mv1! l) Synthesis of ((avv).-o, o
zoM% (Brxog), =j, (7mMs, (I
s). = 10mM) In the following examples, the reaction was carried out in a glass container that had been sufficiently dried, the interior replaced with dry nitrogen, and a three-way stopcock attached. Perform under air current.

47, /■ (0, CO! mmoln heptylvinyl ether (cvi) is dissolved in λ1 carbon tetrachloride, cooled to -jC, and is first added to l, hiro-bis(l-iodoethoxybutane) (: pxxoBn (2j mmol of 1υ/ln
- Add hexane solution/Fd, then add j mmol of iodine/Jwtl of carbon tetrachloride solution and react for 30 minutes (1/L yield lθO%). This solution i-/jOC
0.2 Jtrtl (349 mol) of methyl vinyl ether (Mvm) ((ta) dissolved in toluene was added thereto, and the mixture was reacted (polymerization rate 100%). In this way, av111io units were A with end blocks each consisting of about 10 units of MVE on either side of a center block consisting of A exhibits different properties.

Note that (11) is 0. /44-221 (/mmol) of Darzivinytetraxybutane (1) t/Q- was dissolved in n-hexane, and 2 equivalents of hydrogen fluoride <
It can be obtained quantitatively by reacting an n-hexane solution of roiv mol/l, j1). Hydrogen iocide can be prepared by well-known methods (e.g. J, POlym.

801, Part C, Volume 7, Page 37, 7 (
ltt)).

Examples - ABA block copolymer, poly(MVB-b-ovB-
Synthesis of b-Mvm) by three-step polymerization method (CMVB), =0. AOM, (HI), = (I,
). = 10niM) 0.2 J d (349 mol) of MVfiiJ, dissolved in 4tm of toluene and 3jC
tO mmol/L n of hydrogen Tatsuka to this.
- Add 0.6 liters of hexane solution, then 2j of iodine
mmol/1) Add 2d t-toluene solution and react for 10 minutes (polymerization rate 100%). Here, 67, Im
Add ovm of g (O,
Polymerization rate: 100%). Furthermore, a solution of 0.23 chu (3 mmol) of MVBtJll/dissolved in toluene was added, and -
The reaction was carried out for 30 minutes at JJC (polymerization rate: 100%). In this way, a block with the same composition as Example/+MVICi(c
VB4-4Mvz). (111w/Mn =hekoλ), and as shown in Examples, it exhibits properties different from those of the AB type four.

Example 3 ABA block copolymer, poly(ovi-b~IVF!
-1) -cVB ) synthesis ((KVFi).=-7,7I M , (BIORiB
), ==j, OmM.

[Il! ]. ==iomy) o,term (hetamylisol) ethyrevinyl ether (zvm) was dissolved in 2M toluene and cooled to -JE''C, and to this was added l,4!-bis(/-iodoethoxy).
2j mmol/ln-hexane solution of (BroI!iB) (li)/ldf was added, then 2 of iodine was added.
j mmol/l Toluene solution 21dt added% 6('
React for minutes (polymerization rate ioo%).

OV'ljt of 110 ~ (Heta mmol) here! Add the solution dissolved in carbon tetrachloride, raise the temperature by 1/jC1, and let the reaction continue for 60 minutes (1i ratio 100%)
. Thus, an ABA poly"'r (iw/in =
/, /I) are obtained.

Example 1 Measurement of cloud point of triblock polymer
The cloud point was measured in methanol using a block.

That is, an O, 2, 1 wt % solution (white turbid) of each polymer was calculated, heated for approximately 1 minute, and the temperature at which the solution became transparent was determined. The results are shown in Table/.

It can be seen that the cloud point of ABA) reblock is much lower than that of AB block, and its dissolution is different from that of AB block.

Claims (1)

[Claims] (1) 1,000 C'HR" -CH (OR1) -) Jf-C
HR transfer-CH(OR') 'J) has structure,
A block polyalkenyl ether copolymer consisting of three or more types of chains and having a molecular weight distribution value defined by /Mn of 3 or less. (Here, R1 and R'' represent -H or -CH, a group. H* and R4 represent different alkyl groups that may be substituted with a hetero group, and s nh''t represents an integer of 2 or more. )