JPS62265313A - Production of living polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to "Method 2 for obtaining living polymers" by polymerizing polar α-olefin monomers and the living polymers obtained by such methods.

This technique, referred to as group transfer polymerization, is both 198
U.S. Pat. No. 4,417,034 to Webster and U.S. Pat.
No. 4,508 by Webster, which was patented in
No. 880 lCgta has been issued. The former are acrylic or maleimide polymers using living polymers and specific organo-silicon, -tin, or -germanium initiators and catalysts or Lewis acids that provide sources of fluoride, cyanide, or azide ions. The invention also claims the production of the above six living polymers from monomers.

The latter is similar, but only uses a source of bifluoride ions as a cocatalyst. In both, a variety of suitable solvents are disclosed for the catalyst, including acetonitrile, which is used at t of 19 moles or more per mole of catalyst; It may be used by many more eagles as a livestock medium.

In the present invention, the term "living polymer" refers to a polymer that contains at least one active end group and is capable of further polymerization in the presence of a heptamer (i or more) and a cocatalyst. The terms "living and 6-living activity" are used herein with the reference sign 6" to distinguish them from their biological meaning.

If group transfer polymerization is employed to obtain more favorable results, it may be desirable to find ways to extend or shorten the lifetime of the "living activity 1" of the polymerization.

This means that the rate of termination reaction in the next 1 reaction is reduced in some way. This, in turn, will result in higher molecular weight, lower polydispersity, and a more controlled and timely cured molecular weight.

Related applications include serial numbers 660,588 and 660.589, filed October 18, 1984; and serial numbers 660,588 and 660.589, filed October 18, 1984;
76.099 issue. U.S. Pat. No. 4,588,795 to Dickar 'l, also patented on May 13, 1986, discloses and patents the use of certain types of oxyanion catalysts in group transfer polymerizations. No. 4,622,372 to Ditzker et al., which was filed on November 11, 1985, discloses the use of acetonitrile or silylated acetonitrile to promote the living activity of such oxyanion catalysts. However, they also include the use in conjunction with certain cross-catalysts, thereby increasing the polymerization rate compared to the rate if all catalysts were effective. It is possible that there may be cases where the

The specifications of the patents and applications mentioned above are specifically incorporated herein by reference.

The present invention is characterized in that at least 181 polar acrylic α-olefinic monomers are bonded under polymerization conditions to (i) at least one active substituted group or active diradical, and in some cases, polymerization 4-coordinated silicon, tin, or organogermanium polymerization initiators, which may have one or more groups that are inert under the conditions (
i1) The pKa of the conjugate acid (DMSO) is about 5 to about 2
(iii) pKa of the conjugate acid (DMSO
) is about 5 to about 24.
- an active compound selected from the group consisting of silylated esters or etherified modified products;
At least 1 equivalent of R3Si- groups (Fl contains 20 carbon atoms) per mole of this compound, without substituents or active radicals
hydrocarbyl groups), optionally containing one or more ether oxygens in its aliphatic segment, and optionally containing one or more functional groups that do not react under heavy conditions. The present invention provides a method for producing a living polymer, in which the living polymer is brought into contact with a living polymerization activity promoter that is not a polymerization initiator.

Preferably, the catalyst is tetra(n-butyl)ammonium 6
-chlorobenzoate (TBA-CB)-E or tetra(n-butylammonium bi-6-bichlorobenzoate) (TBA-biCB), and 1ull is 6-bichlorobenzoate (TBA-biCB).
- trimethylsilyl ester of chlorobenzoate.

The preferred concentration of promoter is at least about 0.1 mole per mole of catalyst, or in the range of about 0.1 to 1 ooo mole;
More preferably, it is between 01 and 200, and then between 5 and 25 or between o2 and 2.5, depending on the case.

Preferred oxyanion catalyst conjugate acids have a pKa (DMSO) of about 6-21, more preferably 8-18. :Has.

Preferably, the pKa of the living activity promoter is equal to or lower than the pKa of the catalyst.

In the method of the invention, the resulting polymer is 1 living" and the polymerization is carried out in the growing or grown polymer at the living ends and the radicals or diradicals described above. Gold IA Y
It is characterized by the presence of a Z moiety or its tautomer at the "non-living" bed end of the polymer.

Monomers useful in this invention are of the formula CH2=C(Y)X; where X is -CN, -CH=CHC(0)X'°); L
-C(○)X'; Y is -H, -CH3, -CN or 1002R, and X car CH=CHC(0)X'
Noto @ Y Bar H or 10H3iX' Bar08i (
R1)5. -R, -OR or -NR'R"i each R1 is independently H, or an aliphatic containing up to 20 carbon atoms,
A hydrocarbyl group which is an alicyclic, aromatic or mixed aliphatic-aromatic group, provided that at least one of the groups in 1:11 is H.
a hydrocarbyl group in which R is an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic group containing up to 20 carbon atoms;
or a polymerizable group containing at least 20 carbon atoms;
Any of these groups optionally contains one or more ether oxygen atoms in its aliphatic segment and optionally contains one or more functional groups that are unreactive under the polymerization conditions; and optionally one or more reactive substituents of the formula -Z'(0)C-C(Yl)=CH2, where 1 is H or CHs and 2' is 0- or NR'. ); each of R' and R' shall be independently selected from 01-4 alkyl;

The initiator used in the polymerization of the present invention is described in US Pat.
, 414,572, 4,524,196, 4,41
Nos. 7,054 and 4,508,880, and co-pending Serial Application No. 660,588,660,
2G in Nos. 589.676.926 and 676.099
It is a silicon-containing initiator. Initiators suitable for use in the present invention are those having the formula % where R1 is as defined above and 2 is an active substituent selected from the group: -3R
, -0P(NR'R")2, -0P(OR+)2, -0
R(O8i (R"ls)]2 and mixtures thereof, where R, l, R', R", X' and Z' are as described above; Z1 is an active substituent -0C=C -R
2; and each of R5 is independently selected from H and hydrocarbyl as defined above for R; (a) at least one of R, R2 and R3 in the initiator is optionally one or more; The above formula −
We are preparing a starting chivalry group which will be Z2-M(R1)3. However, in the above formula, M and B1 are as shown above, and Z2 is a divalent active group selected from the following group, that is, a mixture thereof, where R2, R3, X', Z', m and n are as described above. shall be as specified. However, when Z2 is, M is Sn i or ()e.

(b) R2 and R3 are taken together when z and/or z2 is -Z'-C-C(R2) (RlS)-;

(c) When Z and/or Z2 are -C(R2)-CX', X' and either R2' or R5 are taken together.

The term conjugate acid refers to an acid formed by protonation of a catalytic oxyanion; for example, the conjugate acid of an anion is acetic acid, and the conjugate acid of a diacetate anion is acetic acid dimer. be.

The term pKa of a conjugate acid (DMSO) means the inverse logarithm of the acidity constant of the conjugate acid measured in dimethyl sulfoxide (DMSO) at 25C. Methods for measuring the pKa of various dispersible compounds including oxyacids are described, for example, by F.G. Bordwe (F, C), Bordwe
"Journal of Organic Chemistry" (J, ○rg, Chem) Volume 45, No. 33 by ll) et al.
05 page (i980); Volume 46, page 4327 (i9
1981); Vol. 47, p. 3224 (1982); and Vol. 49, p. 1424 (1984).

Explanation of promotion of living activity by silylated oxyanions Group transfer polymerization (C)TP) is a process in which one monomer unit is continuously bonded to the end of a growing polymer chain, and chain transfer occurs. This refers to a 6-living polymerization without any chain termination. Such a method can be applied to monodispersed polymers (n
w/nn approaches 1.0) and a block polymer with a well-controlled structure. Such spontaneous termination reactions cause premature termination of the polymer chain, which has a negative impact on the resulting polymer.

For example, the molecular weight distribution of linear polymers will be broadened (dispersity will be greater than 1). Linear polymers produced by multiple monomer feeds can exhibit multimodal molecular weight distributions, where the molecular weight at each peak seen in the distribution is equal to the living polymer at the starting point of the continuous monomer feed. Responding to the world of Star-shaped block copolymers (-functional monomers are blocked with small amounts of difunctional monomers, the difunctional monomers are for cross-linking and merging of living chains of monofunctional polymers) There will then be a large amount of low molecular weight junior polymer present, which corresponds to the world of polymer chains that were terminated prior to the addition of the difunctional monomer during the star formation stage. Similarly, even in linear block copolymers, some kind of homopolymer of the starting monomers will be present at the end of the polymerization.

Acetonitrile and silylated acetonitrile were found to enhance the living activity of certain C) TP Toai when used in adjusted amounts. Oxyanions C) Silyl ethers or esters of TP catalysts can also control the living activity of GTP polymerization, and for this function, especially at higher polymerization temperatures, either acetonitrile or silylacetonitrile more effective than

For some purposes, it may be desirable, but not necessary, to combine a silylated oxyanion material with a suitable oxyanion catalyst. For example, trimethylsilyl 6-chlorobenzoate is preferably tetra(n
-butyl) ammonium 3-chlorobenzoate catalyst.

Examples of silylated modifications of oxyanionic compounds which are initiators and are therefore excluded from the scope of the claims are e.g. silylated (2-trialkylsilyl)
Vinegar esters.

The weight average molecular weight and number average molecular weight tJk (MY and Mn, respectively) of the polymerization products in the preparations and controls described below were determined by gel permeation chromatography (()PC)
The polydispersity of the polymer is p
It is determined by x Mw/load n. The peak molecular k (Mp) determined by GPC is also recorded at various stages. The degree of polymerization (Dp) is also recorded for the various monomers used. Unless otherwise noted, the resulting 9-living polymer products were quenched by exposure to humid air or methanol, where the molecular weight was determined.
h) be done.

All temperatures are in degrees. All parts, proportions and percentages are by weight unless otherwise specified.

Preparation 1 Trimethylsilyl-3-chlorobenzoate was placed in a 250-mm round-bottom three-necked flask equipped with a di-I4 condenser, a thermocouple, an N24 capacitor, and a polytetrafluoroethylene (PTEE) coated magnetic stir bar. 05r of 6-chlorofemzoic acid and 56.559 of hexamethyldisilazane were fed. The mixture was heated to 0°C and refluxed for 8 hours at a temperature at which ammonia evolution ceased. The excess hexamethyldisilazane is 50 mm
The reaction mixture was stripped under Hg through a side arm condenser until the temperature of the flask contents reached 125°C.

Control 1 ■ Preparation of hvri'E()DM (Dp-100//Dp-4) star polymer (Dp = degree of polymerization) The monomers and solvent used were prepared as follows. Tetrahydrofuran (THF) was prepared by distillation from sodium/benzophenone prior to its use. Methyl methacrylate) (MMA)
and ethylene glycol dimethacryleni) (EC)
DM) was prepared by passing it through a column of neutral anhydrous alumina - and the sides were drawn for 100 ms.
Distilled from calcium hydroxide under Hg and stored under DC for up to one week. 1-trimethylsiloxy-
1-Methoxy-2-methylpropene was prepared by two spininder band distillations (50 mmHg).

A 250-round-bottom three-loaf flask equipped with a condenser, thermocouple, N2 and vacuum inlets, and mechanical stirrer was dried under vacuum (5 mmHg) using a heating gun and
It was left to cool under a N2 purge. The apparatus was placed in a 50C hot water bath, supplied with 117.5t of THF, and left to reach a constant temperature of 50C. If the constant@ is achieved, add 1.01 to the flask! 0.325 m/m of a 0.353 molar solution of tetra(n-7' thyl)ammonium 3-chlorobenzoate in 1-trimethylsiloxy-1-methoxy-2-methylprotin of M' and T)+F was fed.

Reaction flask Hetetra(n-butyl)ammonium 3-
2 minutes after feeding chlorobenzoate, 1 vDa 6
0.08? A 30 minute supply was started. The reaction temperature was maintained at 50°C±0.5°C during each feed.

The flask contents were maintained at 50C±0.50 for 30 minutes after completion of the QJA feed. At this point, 4
45f of gGDM was fed into the reaction flask over 10 minutes. The reaction flask contents were
It was maintained at 0°C ± 0.7°C. One hour after the end of the EflDM feed, methanol (5-) and toluene (0,4 t) were fed into the flask.

After addition of methanol and toluene, no EC) D detected by high-pressure limb chromatography (HPLC)
Neither M nor Kagami survived. The resulting molecular weight distribution is
Gel permeation chromatography (GPC) operates in two modes. Low molecular weight component (i1,0[)OMp)
is composed of 40% polymer with N content, and the polymer tray component (i8
0.00OMp) consists of the remaining 60% polymer by weight.

Example 1 lv1MA///BC)DM(D
p-100//Dp-4') Preparation of star polymer The monomers and solvent used were prepared as follows. T) (F immediately before its use) Prepared by distillation from IJum/benzophenone. MMA and EC) DM were prepared by passing through a column of neutral anhydrous alumina, and MMA was subsequently
Distilled from calcium hydroxide under +aaHg and 0
It was stored at 0.degree. C. for up to one week. 1-Trimethylsiloquine-1-methoxy-2-methylpropene was prepared by two spinning-pan P distillations (50 mmHg).

A 250 m/3 round bottom three-lobe flask equipped with a condenser, thermocouple, N2 and vacuum inlet, and mechanical stirrer was dried under vacuum (5 MHg) using a heating gun;
N2・? - It was left to cool down below. The device was placed in a water bath at 50 °C, supplied with T5 of 116.01,9 and 50 °C.
0.325 m of a 0.353 molar solution of tetra(n-butyl)ammonium 3-chlorobenzonite in THF, 1-trimethylsiloxy-1-methoxy-2-methylpropene 1 .023
9 and trimethylsilyl-5-chloroy in THF/
Sony) (TMS-CB) 0.0961 mol g
1.140 rttl was added. A 30 minute feed of 58.46I MMA was started 2 minutes after the addition of TMS-CB. The reaction contents were kept at 50°C ± 50 minutes during the feeding and for 50 minutes after the end of IIMA feeding.
The temperature was maintained at 0.7°C.

60 minutes after the end of East A supply, 4.61 g of EC)DM was started to be supplied over 10 minutes. During this supply,
The reaction contents were maintained at 50°C±0.5°C.

One hour after the end of the E()DM feed, methanol (5++t/) and toluene (0,444 g) were fed into the 7 flasks.

Conversion rate of EGDM and MMA (measured by HPLCK)
were 997chi and 99.0%, respectively. The resulting molecular weight distribution (measured by ()PC') has two molars, with a low molecular weight component (7,890 M
o) consists of 26 g of polymer by weight, and the high molecular weight component (i34,000 Mp) consists of the remaining 74 g of polymer by weight. This result corresponds to the high molecular weight component 60 in Control 1.
It is contrasted with chi.

Example 2 Ct#AIMkCD using 'rMs-CB, -4//
Preparation of Co., -100) Monomers and solvents used were prepared as follows. TI(F was prepared by distillation from sodium/benzophenone immediately before its use; MMA was prepared by passing through a column of neutral anhydrous alumina;
It is subsequently distilled from calcium hydroxide (ioomHg
) and stored at 0°C for up to one week. GMA was distilled (4 wHg) and inhibited with 100 pP of nitrogen phenyl sulfide. 1-Trimethylsiloxy-1-methoxy-2-methylpro4 was prepared by two spinning-band distillations (50 mHg).

A 250d round-bottom three-loaf flask equipped with a condenser, thermocouple, N2 and vacuum inlets, and mechanical stirrer was dried under vacuum (5wHg) using a heating gun and injected with N2
/#- It was left to cool down below. The apparatus was placed in a 50°C water bath and supplied with 67.65j9 THF. The solvent was allowed to reach a constant temperature of 50°C, after which 0.0% of 1-trimethyl-siloxy-1-methoxy-2-methylzoloben was added.
539F.

Trimethylsilyl-3-chlorobenzoate 0.032
g, and 0.128 ml of a 0.466 molar solution of tetra(n-butyl)ammonium 3-chlorobenzoate in 'I'E (F) were added. After stirring for 2 minutes, GMA
1,71 was added all at once into the flask. An exotherm of 1.3°C was observed. () 15 minutes after MA addition, 30.
Feeding of 25# MMA over 30 minutes was started. The flask contents were maintained at 50.4°C ± 0.4°C during each side feed and until 10 minutes after the MMA feed. One hour after the end of MMA supply, methanol (51t
l) and toluene (0,442,9) were added to the flask.

The conversion rates of GMA and MMA were determined to be 100% and 840%, respectively (determined by HPLC). The resulting molecular weight distribution (measured by GPC) has low molecular weight microprotrusions (15 = 1.982), the low molecular weight component (i, 500 Mp) consists of 2 units of polymer by weight, and the high Molecular weight component (22, DOOMp)
consists of the remaining 98% polymer by weight. After functionalization of the epoxy groups with benzoic acid (preparation example 2), a molecular weight distribution with two modes P (D=3.422) was detected by Teno-Uv test on GPC. Low molecular weight component (2,a O
OM,) contains 43.5% benzoic acid, while the high molecular weight component (i9, OOOMT)) contains the remaining 56.5%. The same sample showed a similar molecular weight distribution (as measured by RI test on a PC) to the original sample. In this way, in Control 2, the 100th section of C)) iA is MM
Compared to the fact that the reaction was terminated before the addition of A, only 43.5% of the GM octopolymer was terminated before the addition of MMA.

Preparation 2 Reaction of GMA//Komibutsu (D Yuichi 6 Otsho Yu-100) Copolymer with Benzoic Acid The CMM/MMA copolymer (prepared in Example 2) was functionalized with benzoic acid as follows. Ta.

In a 500-meter three-necked flask equipped with a thermometer, reflux condenser, and a PTFE-coated magnetic stir bar, 67.4
C) MA-m copolymer solutions (Examples 4 and 5)
91 of benzoic acid, 100 WLl of toluene and 100-propylene carbonate were fed. This solution was heated to reflux with a heating mantle. By the time the reflux temperature reaches 140°C, approximately 110-
of solvent was released. The remaining contents were refluxed at 140° C. for 3 hours.

At this point, 98.8% of the original epoxy content had disappeared (by oxidation titration).

Control 2 GMv8μ to Dp-4Dp-100) Preparation of Copolymer The monomers and solvent used were prepared as follows. TE (F is just before its use) IJum/be/
It was prepared by distillation from siphenon. M
MA was prepared by passing through a column of neutral anhydrous alumina and subsequently distilled from calcium hydroxide (i00 mHg).

It was then stored at 0°C for less than one week. Glycidyl methacrylate (GMA) was distilled (4 Hg) and quenched with 1100 pp of t-Proxymethyl-phenyl sulfide. 1-Trimethyl-siloxy-1-methoxy-2-methylpropene was prepared by two spinning-pan P distillations (50 ■Hg).

250mA with condenser, thermocouple, N2 and vacuum inlet, and mechanical stirrer! A three round bottom flask was dried under vacuum (5 mHg) using a heat gun and allowed to cool under N2/armpit. The apparatus was placed in a 50° C. water bath and supplied with 68.20 g of T[(F).

The solvent was left to reach a constant temperature of 50°C, after which a 0.466 molar solution of 0.543N 1-trimethylsiloxy-1-methoxy-2-methylpropene and tetra(n-'butyl)ammonium 3-chlorobenzoate was added. 1
28 m/ was added. After stirring for 2 minutes, add 1
．． 631 GMA were added all at once. An exotherm of 1.8°C was observed. 30 minutes after GMA was added.
．． A feed of 051 MMA was started over a period of 30 minutes. The contents of the flask were maintained at 50.3°C ± 0.3°C during each A feed and for 10 minutes thereafter. One hour after the MMA feed ended, methanol (5-) and toluene (0,443 fi) was added to the flask.

The conversion rates of GMA and MMA were determined to be 100% and 87.0%, respectively (determined by HPLC).

The resulting molecular weight distribution (determined by GPC) has a molar of two (c=4.675), with the low molecular weight component (i,700M,) consisting of 6% polymer by weight and the high - The cotyledon component (95,000M) consists of the remaining 94% polymer by weight.

To distinguish the epoxy-containing polymer (m-containing) from the block copolymer and the homo-polymer, the remaining niboxy groups in the polymer were reacted with benzoic acid (Preparation 2).

The ultraviolet (UV) method will detect only the benzoate ester present on the GMA-containing, 161J mer, while the refractive index (RI) method will detect any holmer species present. () UV method and RI on PC output stream
In combination with the method, homogenization present in the polymer mixture
o It becomes possible to determine the amount of MA and block copolymer.

After functionalization reaction of epoxy groups with benzoic acid, GP
The molecular weight distribution of a single moo P (D
= 1.421) was detected. Molecular weight of this substance: is 2
．． It was 700M. The same sample had R on OPC
I showed a molecular weight distribution with two 7-Ps, which was identical to that of the original sample. This shows that all of the OMA-homopolymer reacted with I after the addition of M)JA.

Control 3 Preparation of MMA (Dp-200) Linear Homopolymer with Multiple Monomer Feeds MMA was prepared by a chromatographic method through neutral anhydrous alumina and incubated at 0° C. without polymerization inhibitor for up to 2 weeks. Stored for a while. Immediately before its use, THF is added with sodium/
It was prepared by distilling benzophenone. 1-trimethylsiloxy-1-methoxy-2-methylpropylene was subjected to two rounds of spinning par/r distillation (50 m+H
g).

2 equipped with a condenser, heat, N2 and vacuum inlets, addition funnel, heating mantle, and mechanical stirrer.
A 50mJ round-bottomed three-lobe flask is vacuumed using a heating gun (
5 mHg) and allowed to cool under N2. THF' with an eK of 104.01.9 was fed to this equipment and heated to reflux temperature (679°C). Once under reflux, add a 3.1036 molar solution of trimethylsilylacetonitrile (
A 0.8- and 0.466-mole solution of tetra(n-butyl)ammonium 3-chlorobenzoate ('I'BA-CB) in THF (0.172 g of TE (in F) was fed to the flask. Sarani 0.6750.9 in flask
of 1-trimethyl 70xyl-1-methoxy-2-methylpropene initiator was fed. Immediately after supplying the initiator,
19.85.9 MMA feed over 20 minutes was started. While monomer supply continues, the reflux temperature is 68.0
The temperature rose from 68.3°C to 68.3°C. The reaction mixture was kept at reflux temperature (68,0 °C) for 60 min, after which a sample (A) was taken for molecular weight determination and a second MJAA
Feed (20.201 over 20 minutes) was started. The reflux temperature increased from 67.8 to 698° C. as the monomer feed continued. The reaction mixture was again maintained at reflux temperature (710 °C) K for 60 min, after which sample IB) was removed for molecular weight determination and a third MMA feed (20
2o, 1sII) was started over a period of minutes. During the continuation of this monomer feed, the reflux temperature ranged from 69.6 to 71.9°C -4
It rose. The reaction mixture was heated at reflux temperature (7
1,5 °C) after which the sample (C) was removed for molecular weight determination and a fourth MkAA feed (20
20.25.9) was started. During this monomer feed, the reflux temperature rose from 71.6 to 76.9°C. After the fourth monomer has been fed, the reaction mixture is 1
The heating mantle was then removed and the mixture was allowed to cool to room temperature for 60 min before 5 at methanol and 0.444 JF toluene were added and the sample (DJ was used for molecular weight determination). It was taken out.

The molecular weight distribution of each sample was determined by OPC and control 3
A - This is 2x silylated acetonitrile (TMS-C
H3CN) is used, but the results are summarized in Table 1 along with the results for -.

Example 3 Trimethylsilyl-3-chlorobenzoate (TMS-
M! by multiple monomer feedings using CB)! I(
D, -200) Preparation of linear homopolymers MMA was prepared by a chromatographic method through neutral anhydrous alumina,
and stored at 0° C. without polymerization inhibitor for up to 2 weeks. THF was prepared by distillation from sodium/benzophenone immediately before its use. 1-trinotylsiloquine-1-methoxy-2-methylprohair)
(2-subinine f -hay)"y"A';? i(5
0wn) (g, 51 manufactured by iK.

2 equipped with condenser, thermocouple, N2 and vacuum, feeding port, addition funnel, heating mantle, and mechanical stirrer
A 50m1 round-bottom three-bottle flask is heated to a vacuum (
5 mHg) and allowed to cool under N2 gas. 105.3 g of 'f'HF was fed into the apparatus and heated at reflux temperature (619°C)'1. Once under reflux, dissolve 0.1036 molar of trimethylsilylacetonitrile (in Tl1F) overnight in 0.8 m of TMS-CB.
04 molar solution (T) in IF) O, lW and TBA-
0.d66 molar solution Q of CB(TE (in F), 172π
1 was added to the flask. Add another 0.6 to the flask.
92.9 1-trimethylsiloxy-1-methoxy-2
- Methylpropene initiator was supplied. Immediately after the initiator feed, 20.08 II of MlIV4A was started over a 20 minute period. While monomer feed continued, the reflux temperature increased from 679 to 69°C. The reaction mixture is 6
The sample was kept at reflux temperature (68,5 °C) for 0 min, after which a sample (80) was taken for molecular weight determination and the second L (MA feed (2CJ over 20 min, D81) was started). During the continuation of the monomer feed, the reflux temperature increased from 677 to 69,5 °C. The reaction temperature was again maintained at the reflux temperature (68,7 °C), after which a sample (B) was taken for molecular weight determination. , and the sixth MMA supply (
20.20g) was started over 20 minutes. During the continuation of this monomer feed, the reflux temperature rose from 67.9 to 70.5°C. The reaction mixture was heated at reflux temperature (6
92°C) after which sample (C) was removed for molecular weight determination and the fourth MMA feed (19.7!IM over 20 minutes) was started. During the continuation of this monomer feed, the reflux temperature increased from 67.9 to 70.4°C. After the fourth monomer has been fed, the reaction mixture is maintained at reflux temperature for 10 minutes, after which the heating mantle is removed and the mixture is allowed to cool to room temperature for 60 minutes.
5 at methanol and 0.442.9 toluene were then added and a sample (DJ) was taken for molecular weight determination. The molecular weight distribution of each sample was determined by GPC and Example 3A - This The results are summarized in Table 1, along with the results for when acetonitrile was not used. This result shows that the polymerization was living during all four monomer feeds and that the molecular weight was close to the theoretical value. In view of this, the first
This also shows that the death (inactivation) of polymer chains during the supply of the second monomer is extremely small.

Control 4 MMνΔGDM (D
p-100 -4) Preparation of star polymer The star polymer and solvent used were prepared as follows. THF
prepared by distillation from 17 um/benzophenol (purified.contains and EC) D
M is prepared by passing through a column of neutral anhydrous alumina, and MIJ& is followed by 100++ mHg
Distilled from calcium hydroxide below, and 1 below 0 °C
Stored for less than a week. 1-trimethylsiloxy-1
-Methoxy-2-methylpropene is spun twice-
Prepared by Pan P distillation (50 mHg).

A 250 m/3 round bottom three-loaf flask equipped with a condenser, thermocouple, N2 and vacuum inlet, and mechanical stirrer was dried under vacuum (5+mHg) using a heating gun and
It was left to cool down to a temperature of N2/1. The apparatus was fitted with a heating mantle and supplied with 60.6N THF to heat to reflux temperature (67°C). Add 0.550.9 of 1-trimethyl 70x- to the flask under reflux.
0.1 of 1-methoxy-2-methylpropene, tetra(n-butyl)ammonium acetate ('rBAAC)
1575 tJ of molar solution (in TFLF) was fed. T
2 minutes after adding BAAC', 30.40
．． ! 1 of i'. Supply of QJA began over a period of 30 minutes. The reaction was maintained at reflux temperature during each feed and until 60 minutes after the end of the lv1MA feed. At this point, 2.70.9 g of EGDM was fed into the reaction flask over 10 minutes. The reaction flask contents were maintained at reflux temperature for an additional 5 minutes after Ef) DM donor. The flask was then allowed to cool to room temperature over 55 minutes, at which point the reaction was quenched with methanol (5d).

Toluene (0,442 g) was added to the flask at this point.

The conversion rates and molecular weight distributions of MMA and EC)DM are summarized in Table 2.

Example 4 MMν:/11()DM(U-100//D-4) under reflux using TMS-AC and TEAAC
Preparation of Star Polymers The monomers and solvents used were prepared as follows. THF was prepared (purified) by distillation from sodium/benzophenone immediately before its use. MMA and EC) DM were prepared by passing through a column of neutral anhydrous alumina and subsequently distilled from calcium hydroxide under 100 mHg and stored at 0° C. for up to one week.

1-Trimethylsiloxy-1-methoxy-2-methylpropene was subjected to two spinin Durban P distillations (50 mHg).
It was plied by.

A 250 mJ round-bottom three-lobe flask equipped with a condenser, thermocouple, N2 and vacuum inlets, and a mechanical stirrer was dried under vacuum (5 mmHg) using a heating gun and under N2/#- It was left to cool. The apparatus was fitted with a heating mantle and supplied with 58321 THF and heated to reflux temperature (67°C). Add 0.5701 of 1-trimethylsiloxy to the flask under reflux.
0.1 of 1-methoxy-2-methylpropene, tetra(n-butyl)ammonium acetate (CTBAAC)
A 0.575 molar solution (in THF) and a 0.88 molar solution of trimethylsilyl acetate (TMSAC) (T
(in HF) was supplied at 0.183 aa/. Two minutes after TMSAC was added, the 60 minute feed of 30.92F MMA was started. The reaction was maintained at reflux temperature during each feed and until 30 minutes after the end of the feed. At this point 2.60, F
of EC)DM was fed into the reaction flask over a period of 10 minutes. The reaction flask contents were maintained at reflux temperature during the EGDM feed and for an additional 5 minutes thereafter. The flask was then allowed to cool to room temperature over a period of 55 minutes.

At this point the reaction was quenched with methanol (5++tj). At this point toluene (o, 442 g) was added to the flask.

The conversion rate and molecular weight distribution of MMA and EGDM are
The results of Examples 4a and 4b, which use various amounts of TMSAC, are summarized in Table 2. These results demonstrate that when TMSAC is added to the reactants, TMSAC This shows that the polymerization was more living at the beginning of the EGDM feed than in Control 4, where no EGDM was used. These examples and controls demonstrate that yield control, conversion rate, and improvement in unbound molecules are affected by the amount of TMSAC used.

All examples (4, 4a and 4b) showed low conversions and eventually ran out over time.

Control 5 MMA under reflux with TEACB, '/E(
) DM (Dp-100//Dp-4) Cracking of Star Polymers The monomers and solvents used were prepared as follows. THF was prepared (purified) by distillation from IJum/benzophenone immediately before its use. ) HAHA and EGDM were prepared by subjecting a column of neutral anhydrous alumia to '+fji, +1'M, distilled from hydroxide cal/ram under 100 mnHg following i k >g/A, and at 0 °C. Stored for less than one week. 1-Trimethylsiloxy-1-methoxy-2-methylpropene was prepared by two spin-pan distillations (50 as+) (g).

A 250 m/3 round bottom three-loaf flask equipped with a condenser, thermocouple, N2 and 9 fathom inlets, and a mechanical stirrer was dried under vacuum (5 Hg) using a heating gun;
It was left to cool under N2.9-di. The apparatus was equipped with a heating mantle and 59.20 g of THF was fed and heated to reflux temperature (67°C). In the flask,
An additional 0.701 g of 1-trimethylsiloxy-
1-Methoxy-2-methylzoloben and tetra(n-
butyl) ammonium 3-chlorobenzoate (TBA
0.38 molar solution of CB) in TFIF 0.150
ml was supplied. Two minutes after TEACB was added, a 60 minute period of supply of iMA was started at 30.49.9. The reaction was maintained at reflux temperature during each feed and until 30 minutes after the end of the V[MA feed. At this point 2.60.9 Ec) DM
was fed into the reaction flask over a period of 10 minutes.

The reaction flask contents were maintained at reflux temperature for an additional 5 minutes after the E()DM donor.

The flask was then allowed to cool to room temperature over 55 minutes, at which point the reaction was quenched with methanol (5 rttl). At this point, toluene (0,44
6N) was added to the flask.

Conversion rate and molecular weight distribution of DM (French and EC) are the second
A summary is given in the table.

Example 5 MIMA/7'EoI)i((Dp-100//U-) under reflux with TBACB and TMSAC
4) Preparation of star I remer The monomers and solvent used were prepared as follows. T[(F) before its use was prepared (purified) by distillation from IJum/benzopheno/. MMA and EC) DM was prepared by passing through a column of neutral anhydrous alumina, and MMA was subsequently distilled from calcium hydroxide under 100100 nm and stored at 0° C. for up to one week. 1-Trimethylsiloxy-1-methoxy-2-methylpropene was prepared by two spininder band distillations (50 order Hg).

A 250M round-bottom three-loaf flask equipped with a condenser, thermocouple, N2 and vacuum inlets, and a mechanical stirrer was dried under vacuum (5 mHg) using a heating gun and injected with N2
・It was left to cool under a gusset. A heating mantle is attached to this device and 58.20! i of THF was fed and heated at reflux temperature (67° C.). Add 0.580.901-trimethylsiloxy to the flask under reflux.
1-methoxy-2-methylpropene, tetra(n-butyl)ammonium 3-chlorobenzoate (TEACB
) f7) 0.38 molar solution (in THF) 0.150 d
and 0 of trimethylsilyl acetate (TMSAC)
．． An 88 molar solution (in THF) of 0.325 at was fed. Two minutes after the TBACB t, < addition, 30.26.9 upper νfl, 4A supply over 30 minutes was started. The reaction was maintained at reflux temperature during each feed and until 60 minutes after the end of the MMAM feed. At this point, the EGDM of 2.55F is 10
It was fed into the reaction flask over a period of more than a minute. The reaction flask contents were added to the EC) DM donor and then further
The temperature was maintained at reflux for up to 30 minutes. The flask was then allowed to cool to room temperature over 55 minutes, at which point the reaction was quenched with methanol (5 ml aliquot). Toluene (45 g of o, a) was added to the flask at this point.

The conversion rate and molecular weight distribution of MMA and EGDM are
A summary is given in the table. Comparing these results with Control 5, under these atmospheres the silylated oxyanion catalyst - which is a stronger GTP oxyanion catalyst than the one used for polymerization (which exhibits a higher pKa in DMSO) ) indicates that the addition of - does not improve the living activity of ()TP polymerization.

The results show that the polymerization is more viable at the beginning of the EGDM feed, as seen by the higher molecular weight and fractional unbound molecule content than in Control 5, where IMSAC was not used.
(living) not present: However, it teaches that they are equivalent in terms of monomer conversion.

Example 6 Preparation of MMVβGDM (D, -100//勺, -4) Star Polymer under Reflux with IMSCB and TBAAC The monomers and solvent used were prepared as follows. THF was prepared immediately before its use by distillation from IJ/benzophenone. MMA and EGDM were prepared by passing through a column of neutral anhydrous alumina, and MM
A was then distilled from calcium hydroxide under ioam) (g) and stored at 0° C. for up to one week.

1-Trimethylsiloxy-1-methoxy-2-methylpropene was prepared by two-spin Derband distillation (50 mHg).

A 250M round bottom three-lobe flask equipped with a condenser, thermocouple, tJ2 and vacuum inlet, and mechanical stirrer was dried under vacuum (5 mHg) using a heating gun and
N2・! - It was left to cool down below. The apparatus was fitted with a heating mantle and supplied with 59.42.9 kg of THF and heated to reflux temperature (67°C) t. The flask was further charged with a 0.1 molar solution of 0.530.901-trimethylsiloxy-1-methoxy-2-methylprope/tetra(n-butyl)ammonium acetate (TH
F in ) 0.575 m/ and 0.11 molar solution of trimethylsilyl 3-chlorobenzoate (TMSCB) (
1.3M in THF) was supplied. Two minutes after the addition of TBACB, a 30 minute feed of 30.437 MMA was started. The reaction was maintained at reflux temperature during each feed and until 30 minutes after the end of the MMA feed. FC of 2.60y at this point
) DM was fed into the reaction flask over a period of 10 minutes. The reaction flask contents were maintained at reflux during the 800M feed and for an additional 5 minutes thereafter. The flask was then allowed to cool to room temperature over 55 minutes, at which point the reaction was quenched with methanol (5d). At this point toluene (o, 445N) was added to the flask.

The conversion rate and molecular weight distribution of MMA and EGDM are
A summary is given in the table. Comparing these results with Control 4 shows that the silylated oxyanion - which is a weaker GT than used for polymerization - shows that the obtained molecular weight is close to the theoretical value and there are fewer unbound molecules.
It has been shown that the addition of a P-oxy7 anion catalyst (which exhibits a lower pKa in DMSO) improves the living activity of ()TP polymerization.

Claims (1)

[Scope of Claims] 1) At least one polar acrylic α-olefinic monomer is polymerized under polymerization conditions to which (i) at least one active substituent or active diradical has been bonded, and a four-coordinated organosilicon, organotin, or organogermanium polymerization initiator, optionally having one or more substituents that are inert under the polymerization conditions; (ii) a conjugate acid; (iii) the conjugate acid has a pKa (DMSO) of about 5 to about 24; 5 to about 24 o-silylated esters or etherified modifications of oxyanion compounds having no active substituents or active diradicals attached thereto; containing at least one equivalent of an R_3Si- group (R being hydrocarbyl of up to 20 carbon atoms) and optionally containing one or more ether oxygens in its aliphatic segments; 1. A method for producing a living polymer, which is characterized in that it is brought into contact with a polymerization living activity promoter, which is not a polymerization initiator, and which contains one or more functional groups that do not react under polymerization conditions. 2) The method for producing a living polymer according to claim 1, wherein the polymerization initiator (i) is a four-coordinated organic silicone. 3) Claim 1 in which the accelerator (iii) contains the same R_3Si- group as in the polymerization initiator (i)
The method for producing a living polymer as described in Section. 4) The promoter (iii) is a polymerization catalyst oxyanion (ii)
2. The method for producing a living polymer according to claim 2, which comprises a silylated modified product of ). 5) A process for producing a living polymer according to claim 1, wherein the concentration of promoter (iii) present is at least about 0.1 mole per mole of catalyst. 6) The concentration of promoter (iii) is approximately 0.1 per mole of catalyst.
The method for producing a living polymer according to claim 5, wherein the amount is in the range of 200 to 200 moles. 7) A process for producing a living polymer according to claim 6, wherein the concentration of promoter (iii) ranges from about 5 to 25 moles per mole of catalyst. 8) The concentration of promoter (iii) is approximately 0.2 per mole of catalyst.
7. The method for producing a living polymer according to claim 6, wherein the amount is in the range of 2.5 to 2.5 moles. 9) Process for producing a living polymer according to claim 1, wherein the catalyst (ii) is a suitable source of 3-chlorobenzoate and the promoter (iii) is a trimethylsilyl ester of 3-chlorobenzoate. . 10) The living organism according to claim 1, wherein the conjugate acid of the living activity promoter (iii) has a lower pKa (DMSO) than the pKa (DMSO) of the conjugate acid of the catalyst (ii). Polymer manufacturing method.