JPH034563B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polymerization process for polymerizing polar alpha-olefin monomers to obtain "living" polymers, and to the "living" polymers obtained by such processes. This technique, known as group transfer polymerization, was first published in US Pat. No. 4,417,034 to Webster and US Pat.
The same number by Webster, which was patented on the 2nd of May.
Described in No. 4508880. The former is “living room”
The above “living process” from acrylic or maleimide monomers using polymers and specific organo-silicon, -tin, or -germanium-based initiators and catalysts or Lewis acids as sources of fluoride, cyanide or azide ions. ``Manufacturing of polymers.'' 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 in amounts of 19 moles or more per mole of catalyst; however, acetonitrile is also used for polymerization. It may be used in even higher amounts as a conventional solvent. In the present invention, a "living" polymer refers to a polymer that contains at least one active end group and is capable of undergoing further polymerization in the presence of monomer(s) and cocatalyst. The terms "living" and "living active" are used herein with quotation marks "" to distinguish them from their biological meaning. When employing group transfer polymerization to obtain more advantageous results, it would be desirable to find ways to extend or enhance the "living activity" lifetime of the polymerization. This means that the rate of termination reaction in the subsequent polymerization reaction is reduced in some way. This, in turn, will result in higher molecular weights, lower polydispersities, and more controlled and predictable molecular weights. Related applications include serial numbers 660588 and 660589 filed on October 18, 1984; and
There is an application No. 676099 filed on November 29, 1984.
U.S. Pat. No. 4,588,795 to Dicker et al., also issued May 13, 1986, also discloses and claims the use of certain types of oxyanion catalysts in group transfer polymerizations.
No. 4,622,372 to Deitzker et al., issued on November 11, 1985, discloses and claims the use of acetonitrile or silylated acetonitrile to promote the living activity of such oxyanion catalysts. Yes, but they also include the use of certain catalysts, which in some cases may reduce the rate of polymerization compared to the rate if all catalysts were effective. It is uruno. The specifications of the patents and applications mentioned above are specifically incorporated herein by reference. The present invention provides at least one polar acrylic α
- the olefinic monomer is combined under polymerization conditions with (i) at least one active substituent or diradical attached and optionally one or more substituents which are inert under the polymerization conditions; a four-coordinated organosilicon, organotin, or organogermanium polymerization initiator that may have a group, (ii) pKa of the conjugate acid;
(DMSO) is brought into contact with a catalyst which is a salt consisting of about 5 to about 24 oxyanions or bioxyanions and a suitable cation;
and (iii) a trialkylsilyl whose alkyl group has 1 to 20 carbon atoms, which is a type of o-silylated ester of an oxyanion compound whose conjugate acid has a pKa (DMSO) of about 5 to about 24. A method for producing a "living" polymer is provided, which comprises contacting the polymer with a living polymeric activity promoter selected from halobenzoates and trialkylsilyl acetates. Preferably, the catalyst is tetra(n-butyl)ammonium 3-chlorobenzoate (TBA-CB) or tetra(n-butylammonium-3-bichlorobenzoate (TBA-biCB)) and the promoter is trimethylsilyl-3-chlorobenzoate (TBA-biCB). -chlorobenzoate.The preferred concentration of promoter is at least about
0.1 moles or in the range of about 0.1 to 1000 moles, more preferably 0.1 to 200, sometimes 5 to 25 or 0.2 to 2.5. Suitable oxyanion catalyst conjugate acids are about 6 to 21
, more preferably has a pKa (DMSO) of 8 to 18. Preferably, the pKa of the living activity promoter is the same as that of the catalyst.
Equal to or lower than pKa. In the process of the present invention, the resulting polymer is "living" and the polymerization is carried out in the growing or grown polymer at the "living" end and at the active substituent or diradical of a moiety containing the above-mentioned metal. or its tautomer at the "non-living" end of the polymer. Monomers useful in this invention have the formula CH ₂ =C(Y)
X; where X is -CN, -CH=CHC(O)X' or -C
(O)X'; Y is -H, -CH ₃ , -CN or -CO ₂ R, provided that when X is -CH=CHC(O)X', Y is -H or -CH ₃ ; -OSi( ^R1 ) ₃ , -R, -OR or -NR'R''; each ^R1 is independently H, or aliphatic, cycloaliphatic, aromatic or aliphatic containing up to 20 carbon atoms - A hydrocarbyl group, which is an aromatic mixed group, provided that
at least one of R ¹ shall be H; R is aliphatic, cycloaliphatic, containing up to 20 carbon atoms;
a hydrocarbyl group that is aromatic or a mixed aliphatic-aromatic group, or a polymerizable group containing at least 20 carbon atoms, any of these groups optionally containing one or more in its aliphatic segment. or more, optionally containing one or more functional groups that do not react under the polymerization conditions, and optionally also having the formula -Z'(O)C-C (Y ¹ )=One or more reactive substituents represented by CH ₂ (Y ¹ is H or
CH ₃ and Z' is O or NR'; each of R' and _R '' shall be independently selected from C _1-4 alkyl. The initiators described in U.S. Pat. No. 4,414,372, U.S. Pat.
4508880, and co-pending serial application numbers 660588, 660589, 673926 and 676099. Initiators suitable for use in the present invention have the formulas (R ¹ ) ₃ MZ, (R ¹ ) ₂ M(Z ¹ ) ₂ and O[M
⁽ _R ¹ _{) 2}

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] −SR, −OP(NR′R″) ₂ , −OP(OR ¹ ) ₂ , −OR[OSi(R′) ₃
] ₂
and mixtures thereof, where R, R ¹ ,
R′, R″, X′ and Z′ are as described above; Z ¹ is an active substituent

[Formula] m is 2, 3 or 4 N is 3, 4 or 5 M is Si, Sn, Ge. However, Z

[expression] or

when M is Sn or Ge, and each of R ² and R ³ is independently selected from H and hydrocarbyl as defined for R above; (a) in the initiator; At least one of R, ^R2 , and ^R3 optionally includes one or more starting substituents of the formula ^-Z2 -M( ^R1 ) ₃ . However, in the above formula, M and
R′ is as described above, and Z ² is a divalent active group selected from the group below, i.e.,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

and mixtures thereof where R ² , R ³ , X', Z', m and n are as described above. However, Z ² When , M is Sn or Ge. (b) Z is

[Formula] or -OC=C(R ² ) (R ³ ) and/or Z ² When R ² and R ³ are together It is. (c) Z is

[expression] or

[Formula] and/or Z ² is When X′ and either R ² or R ³ are together It is. The term conjugate acid refers to an acid formed by protonation of a catalytic oxyanion; for example, the conjugate acid of an acetate anion is acetic acid, and the conjugate acid of a diacetate anion is acetic acid dimer. be. The term pKa of the conjugate acid (DMSO) means the antilogarithm of the acidity constant of the conjugate acid measured in dimethyl sulfoxide (DMSO) at 25°C. Methods for measuring the pKa of various acidic compounds, including oxyacids, are described, for example, by F.G. Boardwell (F.
“Journal of Organic Chemistry” (J.Org.Chem) Volume 45 by G. Bordwell et al.
Page 3305 (1980); Volume 46, Page 4327 (1981);
Vol. 47, p. 3224 (1982); and Vol. 49, p. 3224 (1982);
1424 pages (1984), etc., and is described in various ways in the literature. Explanation of promotion of living activity by silylated oxyanions Group transfer polymerization (GTP) is a process in which monomer units are continuously bonded to the ends of a growing polymer chain, and there is no chain transfer and ideal Generally speaking, it refers to "living" polymerization without chain termination. Such a method is
If even the spontaneous termination reaction could be controlled, it would be possible to obtain monodisperse polymers (w/n approaching 1.0) and block polymers with well-controlled structures. Such spontaneous termination reactions cause premature termination of the polymer chain, which has various effects on the resulting polymer. For example, the molecular weight distribution of linear polymers will be broadened (dispersity will be greater than 1). Linear polymers made with multiple monomer feeds can exhibit multimodal molecular weight distributions, where the molecular weight at each peak seen in the distribution is equal to the molecular weight at the starting point of each successive monomer feed. Corresponds to the amount of living polymer. For star block copolymers (a monofunctional monomer is blocked with a small amount of a difunctional monomer, the difunctional monomer is for crosslinking the living chains of the monofunctional polymer): There will be a large amount of low molecular weight polymer present, which corresponds to the amount of polymer chains terminated prior to the addition of the difunctional monomer in the star formation stage. Similarly, for 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 GTP polymerizations when used in controlled amounts. Silyl ethers or esters of oxyanion GTP catalysts are also capable of controlling the living activity of GTP polymerization and are more effective at this function than either acetonitrile or silylacetonitrile, especially under higher polymerization temperatures. Effective. For some purposes, it may be desirable, but not necessary, to combine a silylated oxyanionic material with a suitable oxyanionic catalyst. For example, trimethylsilyl 3-chlorobenzoate is preferably used with tetra(n-butyl)ammonium 3-chlorobenzoate catalyst. Examples of silylated modifications of oxyanionic compounds which are initiators and are therefore excluded from the framework of claim (iii) are, for example, silylated (2-trialkylsilyl)acetic esters. The weight average and number average molecular weights (Mw and n, respectively) of the polymerized products in the preparations and controls described below were determined by gel permeation chromatography (GPC). The polydispersity of the polymer is determined by =w/n. The peak molecular weight (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 specified, the resulting "living" polymer product is
It is quenched by exposure to humid air or methanol before the molecular weight is determined. All temperatures are in degrees Celsius. All parts, proportions and percentages are by weight unless otherwise specified. Preparation 1 Preparation of trimethylsilyl-3-chlorobenzoate In a 250 ml round bottom three neck flask equipped with a condenser, thermocouple, _N2 inlet and polytetrafluoroethylene (PTEE) coated magnetic stir bar.
38.05g of 3-chlorobenzoic acid and 56.53g of hexamethyldisilazane were fed. The mixture was heated to reflux temperature and refluxed for 8 hours until ammonia evolution ceased. Excess hexamethyldisilazane was stripped from the reaction mixture under 50 mm Hg through a side arm condenser until the temperature of the flask contents reached 125°C. Control 1 Preparation of MMA//EGDM (D _P -100//D _P -4) Star Polymer (D _P = Degree of Polymerization) The monomers and solvent used were prepared as follows. Tetrahydrofuran (THF) was prepared (purified) by distillation from sodium/benzophenone immediately before its use. Methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) were prepared by passing through a column of neutral anhydrous alumina, and MMA was subsequently distilled from calcium hydroxide under 100 mm Hg and 1 ml at 0 °C. Stored for less than a week. 1-trimethylsiloxy-1-
Methoxy-2-methylpropene was prepared by two spinning-band distillations (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round-bottom three-necked flask equipped with a mechanical stirrer was vacuumed (5 mm Hg) using a heating gun.
The mixture was dried and allowed to cool under a _N2 purge. The device was placed in a 50°C water bath, supplied with 117.5 g of THF, and left to reach a constant temperature of 50°C. Once constant temperature was achieved, the flask was charged with an additional 1.015 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and tetra(n-butyl)ammonium 3-chlorobenzoate in THF.
0.325 ml of a 0.353 molar solution was supplied. Two minutes after feeding tetra(n-butyl)ammonium 3-chlorobenzoate to the reaction flask, MMA60.08
g was started over a period of 30 minutes. The reaction temperature was maintained at 50°C ± 0.5°C during each feed. The flask contents were maintained at 50°C ± 0.5°C for 30 minutes after completion of the MMA feed. At this point, 4.45
g of EGDM was fed into the reaction flask over 10 minutes. The reaction flask contents were maintained at 50°C ± 0.7°C during the EGDM feed. One hour after the end of the EGDM feed, methanol (5 ml) and toluene (0.432 g) were fed into the flask. After addition of methanol and toluene, no detectable EGDM or MMA remained by high pressure liquid chromatography (HPLC). The resulting molecular weight distribution has two modes according to gel permeation chromatography (GPC). The low molecular weight component (11000 M _P ) consists of 40% polymer by weight and the high molecular weight component (180000 M _P ) consists of the remaining 60% polymer by weight. Example 1 MMA//EGDM using TMS-CB ( _DP-
100//D _P -4) Preparation of star polymer The monomers and solvent used were prepared as follows. THF was prepared by distillation from sodium/benzophenone immediately before its use. MMA and EGDM were prepared by passing through a column of neutral anhydrous alumina, and the MMA was subsequently distilled from calcium hydroxide under 100 mm Hg and stored at 0° C. for up to one week. 1-Trimethylsiloxy-1-methoxy-2-methylpropene was prepared by two spinning-band distillations (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round-bottom three-necked flask equipped with a mechanical stirrer was vacuumed (5 mm Hg) using a heating gun.
The mixture was dried and allowed to cool under a _N2 purge. The device was placed in a water bath at 50°C and contained 116.01g of THF.
was fed and allowed to reach a constant temperature of 50°C, then a 0.353 molar solution of tetra(n-butyl)ammonium 3-chlorobenzoate in THF was added.
ml, 1-trimethylsiloxy-1-methoxy-2
- 1.023 g of methylpropene and trimethylsilyl-3-chlorobenzoate (TMS-
1.140 ml of a 0.0961 molar solution of CB) was added.
Two minutes after the addition of TMS-CB, a 30 minute feed of 58.46 g of MMA was started. The reaction contents were maintained at 50°C ± 0.7°C during each feed and for 30 minutes after the end of the MMA feed. Thirty minutes after the end of the MMA feed, 4.61 g of EGDM was started to be fed over a period of 10 minutes. The reaction contents were maintained at 50°C±0.5°C during this feed. One hour after the end of the EGDM feed, methanol (5 ml) and toluene (0.444 g) were fed into the flask. The conversion rates of EGDM and MMA (determined by HPLC) were 99.7% and 99.0%, respectively. Resulting molecular weight distribution (measured by GPC)
has two modes, the low molecular weight component (7.890M _P ) consists of 26% polymer by weight, and the high molecular weight component (134000M _P ) makes up the remaining 74% by weight.
It consists of a polymer of This result is in contrast to the 60% high molecular weight component in Control 1. Example 2 GMA//MMA using TMS-CB (D _P −
4//D _P -100) Preparation of copolymer The monomers and solvent used were prepared as follows. THF was prepared by distillation from sodium/benzophenone immediately before its use. MMA was prepared by passing through a column of neutral anhydrous alumina, subsequently distilled from calcium hydroxide (100 mmHg) and stored at 0° C. for up to one week. GMA was distilled (4 mm Hg) and inhibited with 100 ppm t-butyl-hydroxymethyl-phenyl sulfide. 1-trimethylsiloxy-1-methoxy-2-methylpropene is spun twice.
Prepared by band distillation (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round bottom three neck flask equipped with a mechanical stirrer was dried under vacuum (5 mm Hg) using a heating gun and allowed to cool under a _N2 purge. The device was placed in a 50°C water bath and supplied with 67.65g of THF. The solvent was left to reach a constant temperature of 50°C, then 0.539 g of 1-trimethyl-siloxy-1-methoxy-2-methylpropane, 0.032 g of trimethylsilyl-3-chlorobenzoate, and tetra(n-butyl)ammonium in THF were added. 0.128 ml of 0.466 molar solution of 3-chlorobenzoate
was added. After stirring for 2 minutes, 1.74 g of GMA was added all at once into the flask. A fever of 1.3℃ was observed. 15 minutes after adding GMA, 30.25g of
Delivery of MMA was started over a period of 30 minutes. The flask contents were mixed with MMA feed and
The temperature was maintained at 50.4°C ± 0.4°C until 10 minutes had passed after the MMA supply. One hour after the end of the MMA feed, methanol (5 ml) and toluene (0.442 g) were added to the flask. The conversion rates of GMA and MMA were determined to be 100% and 84.0%, respectively (determined by HPLC). The resulting molecular weight distribution (measured by GPC) is a low molecular weight microprojection (=1.982)
The low molecular weight component (1500 M _P ) consists of 2% polymer by weight, and the high molecular weight component (22000 M _P ) consists of the remaining 98% polymer by weight.
After functionalization of the epoxy groups with benzoic acid (preparation example 2), a bimodal molecular weight distribution (=
3.422) was detected by UV inspection on GPC.
The low molecular weight component (2800 M _P ) contains 43.5% benzoic acid, while the high molecular weight component (19000 M _P ) contains the remaining 56.5%. The same sample is (GPC
(as measured by the RI test above) showed a molecular weight distribution similar to that of the original sample. Thus, in control 2
100% of GMA was quenched before addition of MMA, while 43.5% of GMA homopolymer was
The reaction had simply stopped before the addition of MMA. Preparation 2 Reaction of GMA//MMA (D _P -6//D _P -100) Copolymer with Benzoic Acid GMA//MMA copolymer (prepared in Example 2) was functionalized with benzoic acid as follows. It was done. In a 500 ml three-necked flask equipped with a thermometer, reflux condenser, and PTFE-coated magnetic stirring bar,
67.4 g GMA//MMA copolymer solution (prepared in Examples 4 and 5), 9 g benzoic acid, 100 ml toluene and 100 ml propylene carbonate were fed. This solution was heated to reflux with a heating mantle. Approximately 110 ml of solvent was released by the time the reflux temperature reached 140°C. The remaining contents were refluxed at 140°C for 3 hours. At this point, 98.8% of the original epoxy content had disappeared (by epoxy titration). Control 2 Preparation of GMA//MMA (D _P -4//D _P -100) Copolymer The monomers and solvents used were prepared as follows. THF was prepared by distillation from sodium/benzophenone immediately before its use. MMA was prepared by passing through a column of neutral anhydrous alumina, subsequently distilled from calcium hydroxide (100 mmHg), and stored at 0° C. for up to one week. Glycidyl methacrylate (GMA) is distilled (4 mm
Hg) and polymerization was inhibited with 100 ppm of t-butyl-hydroxymethyl-phenyl sulfide.
1-trimethyl-siloxy-1-methoxy-2-
Methylpropene was subjected to two spinning-band distillations (50
mmHg). A 250 ml round-bottom three-necked flask equipped with a condenser, thermocouple, _N2 and vacuum inlet and mechanical stirrer was heated to a vacuum (5 mmHg) using a heating gun.
The mixture was dried and allowed to cool under a _N2 purge. The device was placed in a 50°C water bath and 68.20g of THF was supplied. The solvent was left to reach a constant temperature of 50°C, after which 0.543 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and 0.128 ml of a 0.466 molar solution of tetra(n-butyl)ammonium 3-chlorobenzoate were added. . After stirring for 2 minutes, 1.63 g of GMA was added all at once into the flask. A fever of 1.8℃ was observed. Fifteen minutes after the GMA was added, a 30 minute feed of 30.05 g of MMA was started. The flask contents were maintained at 50.3°C ± 0.3°C during each MMA feed and for 10 minutes thereafter. One hour after the MMA supply ended, methanol (5 ml) was added.
and toluene (0.443g) were 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 (measured by GPC) has two modes (=4.675),
The low molecular weight component (1700 M _P ) consists of 6% polymer by weight and the high molecular weight component (95000 M _P ) consists of the remaining 94% polymer by weight. To distinguish the epoxy-containing polymer (GMA-containing) from block copolymers and homo-MMA polymers, the remaining epoxy 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 polymer, while the refractive index (RI) method will detect all polymer species present. The combination of UV and BI methods on the GPC output stream makes it possible to determine the amount of homo-GMA and block copolymers present in the polymer mixture. After the functionalization reaction of the epoxy groups with benzoic acid, a unimodal molecular weight distribution (=1.421) was detected by UV examination on GPC. The molecular weight of this material was 2700M _P. The same sample is
Examination by RI on GPC showed a bimodal molecular weight distribution, which was identical to that of the original sample. This shows that all of the GMA homopolymer reacted before the addition of MMA. Control 3 MMA with multiple monomer feedings (D _P −200)
Preparation of Linear Homopolymers MMA was prepared by chromatography through neutral anhydrous alumina and stored at 0° C. without polymerization inhibitor for up to two weeks. THF was prepared by distilling it from sodium/benzophenone immediately after its use. 1-trimethylsiloxy-1-methoxy-2-methylpropene is 2
It was prepared by double spinning-band distillation (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round bottom three neck flask equipped with an addition funnel, heating mantle, and mechanical stirrer was dried under vacuum (5 mm Hg) using a heat gun and allowed to cool under a N ₂ purge. The apparatus was charged with 104.01 g of THF and heated to reflux temperature (67.9°C). of trimethylsilylacetonitrile once under reflux.
0.8 ml of a 0.1036 molar solution (in THF) and a 0.466 molar solution (in THF) of tetra(n-butyl)ammonium 3-chlorobenzoate (TBA-CB)
0.172ml was delivered to the flask. Add another 0.6750 g of 1-trimethylsiloxyl-1- to the flask.
Methoxy-2-methylpropene initiator was provided. Immediately after feeding the initiator, add 19.85 g of MMA to 20
Supply began over a period of minutes. While monomer feed continued, the reflux temperature increased from 68.0 to 68.3°C. The reaction mixture was maintained at reflux temperature (68.0°C) for 60 min, after which sample A was removed for molecular weight determination and a second MMA feed (over 20 min)
20.20g) was started. The reflux temperature increased from 67.8 to 69.8°C while monomer feed continued. The reaction mixture was again maintained at reflux temperature (70.0°C) for 60 min, after which sample B was removed for molecular weight determination and a third MMA feed (over 20 min)
20.15g) was started. During the continuation of this monomer feed, the reflux temperature increased from 69.6 to 71.9°C. The reaction mixture was maintained at reflux temperature (71.5°C) for an additional 60 min, after which sample C was removed for molecular weight determination and a fourth MMA feed (over 20 min)
20.25g) was started. During this monomer feed, the reflux temperature increased from 71.6 to 73.9°C. After the fourth monomer feed was finished, the reaction mixture was maintained at reflux temperature for 10 minutes, after which the heating mantle was removed and the mixture was allowed to cool to room temperature for 60 minutes,
Then 5 ml of methanol and 0.444 g of toluene were added and sample D was removed for molecular weight determination. The molecular weight distribution of each sample was determined by GPC,
Control 3A - This uses 2x silylated acetonitrile (TMS-CH ₃ CN) and is summarized in Table 1 with the results for 1. Example 3 Preparation of MMA (D _P -200) linear homopolymer by multiple monomer feeds using trimethylsilyl-3-chlorobenzoate (TMS-CB) Chromatographic method where MMA is passed through neutral anhydrous alumina and stored below 0° C. without polymerization inhibitor for up to two weeks. THF was prepared by distillation from sodium/benzophenone immediately before its use. 1-Trimethylsiloxy-1-methoxy-2-methylpropene was prepared by 2-spinning-band distillation (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round bottom three neck flask equipped with an addition funnel, heating mantle, and mechanical stirrer was dried under vacuum (5 mm Hg) using a heat gun and allowed to cool under a _N2 purge. The apparatus was charged with 105.3 g of THF and heated to reflux temperature (67.9° C.). of trimethylsilylacetonitrile once under reflux.
0.8 ml of a 0.1036 molar solution (in THF) of TMS-CB
0.8 ml of 0.1104 molar solution (in THF) and TBA−
0.172 ml of a 0.466 molar solution of CB (in THF) was fed to the flask. Add another 0.692 g of 1- to the flask.
Trimethylsiloxy-1-methoxy-2-methylpropene initiator was provided. Immediately after the initiator feed, the feed of 20.08 g of MMA was started over a period of 20 minutes. While the monomer feed continues, the reflux temperature is
The temperature rose from 67.9 to 69℃. The reaction mixture was maintained at reflux temperature (68.5°C) for 60 minutes, after which sample A was removed for molecular weight determination and a second
MMA feeding (20.08 g over 20 minutes) was started. While monomer feed continued, the reflux temperature increased from 67.7 to 69.5°C. The reaction temperature was again maintained at reflux temperature (68.7°C), after which sample B was removed for molecular weight determination and a third MMA
Feed (20.20 g over 20 minutes) was started. While this monomer feed continues, the reflux temperature ranges from 67.9 to 70.5.
The temperature rose to ℃. The reaction mixture was maintained at reflux temperature (69.2°C) for an additional 60 min, after which sample C was removed for molecular weight determination and a fourth MMA
Feed (19.75 g over 20 minutes) was started. During the continuation of this monomer feed, the reflux temperature ranges from 67.9
The temperature rose to 70.4℃. After the fourth monomer has been fed, the reaction mixture is maintained at reflux temperature for 10 minutes;
The heating mantle was then removed and the mixture was allowed to cool to room temperature for 60 minutes before 5 ml of methanol and 0.442 g of toluene were added and Sample D was removed for molecular weight determination. The molecular weight distribution of each sample was determined by GPC and is summarized in Table 1 along with the results of Example 3A, in which no silylated acetonitrile was used. This result is consistent with the polymerization in the first and second monomer feeds than in Control 3, given that the polymerization was living during all four monomer feeds and that the molecular weight was closer to the theoretical value. This shows that chain death (inactivation) is extremely low.

【table】

[Table] Control 4 MMA under reflux using TBAAC//
Preparation of EGDM (D _P -100//D _P -4) Star Polymer The monomers and solvent used were prepared as follows. THF was prepared (purified) by distillation from sodium/benzophenone immediately before its use. MMA and EGDM were prepared by passing through a column of neutral anhydrous alumina, and MMA was subsequently hydroxylated under 100 mmHg. Distilled from calcium and stored at 0°C for up to one week. 1-trimethylsiloxy-1
-Methoxy-2-methylpropene was prepared by two spinning-band distillations (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round bottom three neck flask equipped with a mechanical stirrer was dried under vacuum (5 mm Hg) using a heating gun and allowed to cool under a _N2 purge. This device was equipped with a heating mantle and weighed 60.6 g.
THF was fed and heated to reflux temperature (67°C). The flask was further charged with 0.550 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene, a 0.1 molar solution of tetra(n-butyl)ammonium acetate (TBAAC) (THF) under reflux.
Medium) 0.575ml was supplied. Two minutes after the TBAAC was added, the 30.40 g MMA feed was started over a 30 minute period. The reaction was maintained at reflux temperature during each feed and until 30 minutes after the end of the MMA feed. 2.70 at this point
g of EGDM was fed into the reaction flask over 10 minutes. The reaction flask contents are
It was 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 55 minutes, at which point the reaction was quenched with methanol (5 ml). Toluene (0.442g) was added to the flask at this point. The conversion rates and molecular weight distributions of MMA and EGDM are summarized in Table 2. Example 4 MMA//EGDM (D _P -100//D _P -4) under reflux using TMS-AC and TBAAC
Preparation of Star Polymers The monomers and solvents used were prepared as follows. THF was prepared (purified) from sodium/benzophenone by distillation immediately before its use. MMA and EGDM were prepared by passing through a column of neutral anhydrous alumina, and the MMA was subsequently distilled from calcium hydroxide under 100 mm Hg and stored at 0° C. for up to one week. 1-trimethylsiloxy-1
-Methoxy-2-methylpropene was prepared by two spinning-band distillations (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round-bottom three-necked flask equipped with a mechanical stirrer was vacuumed (5 mm Hg) using a heating gun.
The mixture was dried and allowed to cool under a _N2 purge. This device is equipped with a heating mantle and weighs 58.32g.
of THF was fed and heated to reflux temperature (67°C). Add another 0.570 g to the flask under reflux.
1-trimethylsiloxy-1-methoxy-2-
Methylpropene, 0.575 ml of a 0.1 molar solution (in THF) of tetra(n-butyl)ammonium acetate (TBAAC) and 0.88 molar solution (in THF) of trimethylsilyl acetate (TMSAC)
0.183ml was supplied. Two minutes after TMSAC was added, 30.92 g of MMA was started to be fed over a 30 minute period. The reaction was maintained at reflux temperature during each feed and until 30 minutes after the end of the MMA feed. At this point, 2.60g
EGDM 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 55 minutes, at which point the reaction was quenched with methanol (5 ml). Toluene (0.442g) was added to the flask at this point. The conversion rates and molecular weight distributions of MMA and EGDM are shown in Examples 4a and 4b - These are TMSAC
A summary is given in Table 2 along with the results using various amounts of . These results demonstrate that when TMSAC is added to the reactants, the molecular weight is more controlled, monomer conversion is higher, and there are fewer unbranched molecules (less low molecular weight materials). This shows that the polymerization was more living at the beginning of the EGDM feed than in Control 4, where no TMSAC was used. These examples and controls are
It has been shown that molecular weight control, conversion and improvement for unbranched molecules are affected by the amount of TMSAC used. All Examples 4, 4a and 4b showed low conversion and eventually gelled over time. Control 5 MMA under reflux with TBACB//
Preparation of EGDM (D _P -100//D _P -4) Star Polymer The monomers and solvent used were prepared as follows. THF was prepared (purified) by distillation from sodium/benzophenone immediately before its use. MMA and EGDM were prepared by passing through a column of neutral anhydrous alumina, and MMA was subsequently distilled from calcium hydroxide under 100 mm Hg and 1
Stored for less than a week. 1-Trimethylsiloxy-1-methoxy-2-methylpropene was prepared by two spinning-band distillations (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round-bottom three-necked flask equipped with a mechanical stirrer was vacuumed (5 mm Hg) using a heating gun.
The mixture was dried and allowed to cool under a _N2 purge. A heating mantle is attached to this device and 59.20g
of THF was fed and heated to reflux temperature (67°C). The flask was charged with an additional 0.70 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and tetra(n-butyl)ammonium 3-chlorobenzoate (TBACB) under reflux.
0.150 ml of a 0.38 molar solution (in THF) was provided.
After 2 minutes of adding TBACB, 30.49
A feed of 1 g of MMA was started over a period of 30 minutes. The reaction was maintained at reflux temperature during each feed and until 30 minutes after the end of the MMA feed. At this point, 2.60 g of EGDM 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 55 minutes, at which point the reactants were dissolved in methanol (5
ml). Toluene (0.446g) was added to the flask at this point. The conversion rates and molecular weight distributions of MMA and EGDM are summarized in Table 2. Example 5 MMA//EGDM (D _P -100//D _P -4) under reflux with TBACB and TMSAC
Preparation of Star Polymers The monomers and solvents used were prepared as follows. TEF was prepared (purified) by distillation from sodium/benzophenone immediately before its use. MMA and EGDM were prepared by passing through a column of neutral anhydrous alumina, and the MMA was subsequently distilled from calcium hydroxide under 100 mm Hg and stored at 0° C. for up to one week. 1-Trimethylsiloxy-1-methoxy-2-methylpropene was prepared by two spinning-band distillations (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
A 250 ml round bottom three neck flask equipped with a mechanical stirrer was dried under vacuum (5 mm Hg) using a heating gun and allowed to cool under a _N2 purge. This device was equipped with a heating mantle and weighed 58.20 g.
THF was fed and heated to reflux temperature (67°C). The flask was charged with an additional 0.580 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene, 0.150 ml of a 0.38 molar solution of tetra(n-butyl)ammonium 3-chlorobenzoate (TBACB) in THF and 0.325 ml of a 0.88 molar solution of trimethylsilyl acetate (TMSAC) in THF was provided. After 2 minutes of TBACB addition, 30.26 g of MMA
Supply began over a period of minutes. The reaction was maintained at reflux temperature during each feed and until 30 minutes after the end of the MMA feed. at this point
2.55 g of EGDM was fed into the reaction flask over 10 minutes. The reaction flask contents are
The reflux temperature was maintained during the EGDM feed and for a further 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 (5 ml). At this point, toluene (0.445g)
was added to the flask. The conversion rates and molecular weight distributions of MMA and EGDM are summarized in Table 2. Comparing these results with Control 5 shows that 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) ) shows that the addition of one does not improve the living activity of GTP polymerization.
The results show that the polymerization is less living at the beginning of the HGDM feed, as seen by the higher molecular weight and unbranched molecule content than in Control 5, where IMSAC was not used; however, the monomer conversion was similar. It teaches that Example 6 MMA//EGDM (D _P -100//D _P -4) under reflux with IMSCB and TBAAC
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 EGDM were prepared by passing through a column of neutral anhydrous alumina, and the MMA was subsequently distilled from calcium hydroxide under 100 mm Hg and stored at 0° C. for up to one week. 1-Trimethylsiloxy-1-methoxy-2-methylpropene was prepared by two spinning-band distillations (50 mmHg). condenser, thermocouple, _N2 and vacuum inlet,
and a 250 ml round-bottom three-necked flask equipped with a mechanical stirrer was heated under vacuum (5 mm Hg) using a heating gun.
The mixture was dried and allowed to cool under a _N2 purge. This device is equipped with a heating mantle and weighs 59.42 g.
THF was fed and heated to reflux temperature (67°C). The flask was charged with an additional 0.530 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene, 0.575 ml of a 0.1 molar solution of tetra(n-butyl)ammonium acetate in THF and trimethylsilyl 3-chlorobenzoate under reflux. 1.3 ml of a 0.11 molar solution of (TMSCB) in THF was provided. Two minutes after TBACB was added, 30.43 g of MMA was started to be fed over a 30 minute period. The reaction is fed one by one and further
The temperature was maintained at reflux until 30 minutes after the end of the MMA feed. At this point, 2.60g of EGDM is 10
It was fed into the reaction flask over a period of more than a minute.
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 55 minutes, at which point the reaction was quenched with methanol (5 ml). Toluene (0.445g) was added to the flask at this point. The conversion rates and molecular weight distributions of MMA and EGDM are summarized in Table 2. Comparing these results with Control 4 shows that the silylated oxyanion, which is a weaker GTP oxyanion than that used for polymerization, shows that the molecular weight obtained is close to the theoretical value and there are fewer unbranched molecules. The addition of an anionic catalyst (which exhibits a lower pKa in DMSO) is shown to improve the living activity of GTP polymerization.

【table】

Claims (1)

[Scope of Claims] 1. At least one polar acrylic α-olefinic monomer is added under polymerization conditions to (i) at least one polar acrylic α-olefin monomer;
4-coordinated organosilicon, which has attached active substituents or active diradicals and optionally has one or more substituents which are inert under the polymerization conditions. tin or organogermanium polymerization initiator, (ii) pKa of conjugate acid
(DMSO) is brought into contact with a catalyst which is a salt consisting of about 5 to about 24 oxyanions or bioxyanions and a suitable cation;
Furthermore, (iii) a method for producing a living polymer, which is brought into contact with a polymerization living activity promoter selected from trialkylsilyl halobenzoates and trialkylsilyl acetates in which the alkyl group has 1 to 20 carbon atoms. 2. The method for producing a living polymer according to claim 1, wherein the polymerization initiator (i) is a four-coordinated organosilicon. 3 The concentration of promoter (iii) present is at least about 0.1 mole per mole of catalyst.
The method for producing a living polymer as described in Section. 4. A process for producing a living polymer according to claim 3, wherein the concentration of promoter (iii) ranges from about 0.1 to 200 moles per mole of catalyst. 5 The concentration of promoter (iii) is between about 5 and 1 mole of catalyst.
A method for producing a living polymer according to claim 4, wherein the amount is in the range of 25 moles. 6. A process for producing a living polymer according to claim 4, wherein the concentration of promoter (iii) is in the range of about 0.2 to 2.5 moles per mole of catalyst. 7 Catalyst (ii) is a suitable source of 3-chlorobenzoate and promoter (iii) is trimethylsilyl-
A method for producing a living polymer according to claim 1, which is 3-chlorobenzoate.