JPS6089452A - Compound for manufacturing 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 Field of the Invention The present invention relates generally to improved methods for free radical polymerization, and more particularly to articulating the growth stage of polymerization to produce relatively short chain length homopolymers and copolymers, including block and graft copolymers. The present invention relates to an improved process by which the invention can be carried out, and furthermore to novel polymerization initiators which find particular application in the improved process.

BACKGROUND AND SUMMARY OF THE INVENTION Polyq'-, often referred to as oligomers, with relatively low molecular weights (short chain lengths) have recently become of increasing interest, as such polymers can be used, e.g. Non-reactive intermediates for the production of surface coatings such as minute or solvent-free surface coatings, in adhesives, as plasticizers in polymeric compositions, and for the production of a wide variety of other substances, such as surfactants. This is because it has been found to be useful for various products such as physical goods. 500 to 250
Although various alkyds, polyesters, polyethers, polyamides, and polyurethanes with molecular weights ranging from It was impossible.Fact USA
British Patent No. 1,451,446 to Rohm Hand Haas Corporation in v. Sul teaches: ``
Attempts have been made to create acrylic polymers with molecular weight distributions ranging from 500 to 5000 by free radical polymerization techniques. However, these procedures are generally difficult due to the high temperatures and pressures required to carry out the polymerization reaction, or because the chain transfer agents used in the reaction have unpleasant odors or toxicity, or because the nature of the polymer produced by the polymerization reaction was unsatisfactory either because of the large amount of initiator or chain transfer agent fragments produced on the polymer mirror.

Furthermore, it is difficult to control the molecular weight distribution of polymers made by free radical techniques.

Such polymers therefore tend to have a broad molecular weight distribution and contain significant amounts of high and very low molecular weight polymers, which tend to impart unattractive properties to the polymer composition. As mentioned above, the production of certain oligomers from unsaturated polymers is limited by the techniques available for free radical polymerization and, until the discovery of the present invention, it has not been possible to liberate polymers with chain lengths of 200 monomer units or less. It was difficult to obtain by base polymerization.

Although techniques such as anionic or cationic polymerization can satisfactorily produce orichmers from unsaturated monomers in some circumstances, the harsh reaction conditions required by these techniques are difficult to achieve on an industrial scale. There are, and many moreover, cannot be polymerized by these techniques.

Anionic, cationic, and stepwise growth polymerizations are amenable to controlled growth because they can be stopped after a counterstep. It would therefore be desirable if the control achieved by stepwise polymerization techniques could be achieved by free radical polymerization, but without the inconvenience of harsh reaction conditions.

In the past, the synthesis of block copolymers was practically possible only by anionic synthesis, but very limited monomers could be synthesized using cationic polymerization. The use of sequential addition of monomers in conventional free radical polymerizations means that at the end of each monomer addition step there will be no lipping radicals and new radicals must be created to initiate a new 7-mer polymerization. The need may lead to mixtures of homopolymers. There are other reactions known as rearrangement reactions that have been used to create Zoroku copolymers of the AAABBBB type. One of these is the anionic polymerization of one heptad polymer. Subsequent reaction with bromine provides a bromine-terminated polymer, which is then reacted with silver perchlorate in the presence of a second septamer.

This method is cumbersome and has limited application.

Another method involves anionic polymerization of one heptadmer, followed by conversion of the anion center to a free radical by reaction with trimethyl lead chloride, which upon heating forms a block copolymer mixed with a homopolymer of the second monomer. arise. Other rearrangement reactions are radical polymerization followed by cationic polymerization, or radical polymerization followed by anionic polymerization.

All these methods have the drawbacks mentioned above.

A further development of block copolymers is graft copolymers, which consist of a backbone polymer chain? It is a remer material to which a number of polymer chains are attached and the attached or grafted polymers are chemically different from the backbone polymer chains. As a way of illustration, two monomers A and B can have the following chemical structure: Copolymers of different heptads are possible, such as. Either the single trunk or the grafted chains can be branched.

Due to their structure, graft copolymers have unique properties, especially the chemical bonding of completely different polymeric entities, which makes graft copolymers particularly due to their surfactant properties, which cannot coexist in other situations with the physical properties of polymers or monomer compounds. It is useful in stabilizing commercial formulations. They are of significant industrial interest.

A useful method of making graft polymers is to first create a polymeric backbone or utilize it as a naturally occurring polymeric backbone and then create active polymerization initiation sites at various locations on the backbone polymer and use these sites to create the desired seven polymers. - is polymerized to form a graft chain. Addition polymerization of vinyl septamers, step growth polymerization, or ring opening polymerization of cyclic monomers by free radical or cationic means can be used to create the grafted chains.

A common method of making graft copolymers is free radical polymerization of the grafted chains, creating radical sites on the polymer backbone in the presence of the heptadmer to be grafted. The radicals can be removed by free radicals, by removal of hydrogen atoms from the polymer by irradiation with ultraviolet light or by ionizing radiation, or if the backbone polymer contains a suitable functional group, such as a hydroxyl group, by a Px-based system, e.g.
e”/H2O2. This general procedure usually yields homopolymers as well as the desired graft copolymers. Using this method it is difficult to control the graft bond chain length because the chains This is because once started, it grows extremely rapidly until it is stopped by reaction with other radicals.

Prior art alternatives create reactive monomer units in the polymer chain by copolymerization methods or by chemical treatment of the backbone polymer. For example, acrylic polymers and copolymers can be reacted with phosphorous pentachloride and then reacted with hydroperoxide to form peracid esters. The latter provides free radical sites for grafting upon degradation.

Although direct peroxidation of the backbone polymer with peroxides and hydroperoxides can sometimes be used, attempts to introduce active groups directly into polystyrene by reaction with benzoyl peroxide have not been successful. Direct peroxidation can be achieved if a comonomer containing inpropyl groups is introduced into the polystyrene chain.

It is now possible to produce oligomeric, usually short chain length homopolymers or copolymers by means of controlled propagative free radical polymerization by the process according to the invention and by the process initiated by the compounds according to the invention. It was discovered that.

According to one aspect of the invention, the free radical polymerization of a suitable unsaturated polymer provides an initiator suitable for use in a process for producing polymers, particularly oligomers, which initiator has the formula
has the general structure: (or a group containing at least one carbon atom and the radical X , and the radical functionality is present on the carbon atom or one of the carbon atoms, and R1
, R2, R5 and R6 are identical or different linear or branched substituted or unsubstituted alkyl groups of sufficient chain length to provide steric hindrance and weakening of the ox bond;
and R3 and R4 can be the same or different straight or branched alkyl or substituted alkyl groups or R30NOR4 can be part of a cyclic structure, which is fused to another saturated or aromatic ring. You may do so. ) According to a further feature of the invention, the polymer or copolymer, in particular the oligomer, is prepared by free radical polymerization of a suitable unsaturated polymer comprising heating a compound having the general structure of formula I with suitable monomers. You will be given a way to do so.

Another feature of the invention is directed to the polymers, particularly short chain oligomers, made by the method of the invention.

A further feature of the present invention is that Zoroku copolymers are prepared by the polymerization method of the present invention by alternating the addition of two or more monomers to create a polymer in which each heptad is sequentially linked. It is about giving.

Another aspect of the invention is directed to the production of graft copolymers by the method of the invention and to the graft copolymers so made.

Preferably, weakening of the 0-x bond is achieved at moderate temperatures.

Suitable groups for X are tertiary decyl, cyanoisopropyl, phenyl, methyl or the like. Generally, the structure of Suitable groups for R1, R2, R5 and R6 are methyl, ethyl, propyl, butyl, isopropyl, isobutyl, 1-butyl, neo-pentyl, benzyl or It is similar to.

Suitable groups for R3 and/or R4 are methyl, ethyl, zorogyl, butyl, isozologyl, isobutyl,
and -butyl, pentyl, octadecyl or the like, or if R30NOR4 is part of a cyclic structure, the cyclic structure is: The cyclic structure can be substituted.

For controlled free radical polymerization with an initiator of formula I, the formula ■
It is desirable that the nitroxide groups of the unsaturated monomers themselves do not initiate any substantial free radical polymerization of the unsaturated monomers themselves.

Although the alkoxyamine rainbows of which the compounds of formula (I) form a sub-group are well known compounds, the compounds according to formula I are believed to be novel due to the nature of their substituents.

It has been discovered that hindered alkoxyamines can generally be used as initiators of free radical polymerization according to the present invention at reasonable temperatures. Furthermore, it has been discovered that such a polymerization process proceeds by inserting a monomer unit between the nitroxide group of formula (1) and Xo, ie by a reversible termination method.

This method is referred to herein as growth-controlled free radical polymerization.

Alkoxyamines such as in formula I can be prepared by heating the nitroxide group of formula I in the presence of a stoichiometric amount of a carbon-centered free radical X°, provided that Xo is It can be generated in any known manner, for example by decomposition of azo compounds, by cleavage of alkoxy groups or by removal of hydrogen atoms from suitable monomeric or polymeric compounds or by addition of free radicals to olefins, and especially X”
is X-X, or X-Z-X or X-Z-Z-X (
However, 2 can be generated by thermal or photochemical dissociation of a small stable molecule in its uncombined form, such as a group such as C02 or NH2.

The alkoxyamine so produced can be isolated and purified for later use or used without further purification to initiate the polymerization.

The nitroxide of formula
It can be readily made by oxidation of roxylamines, by reduction of appropriate nitro or nitroso compounds, or by free radical addition to nidrones. Alternatively, alkoxyamine initiators can be created or generated in situ by the addition of a free radical source to a suitable nitroxide in the presence of unsaturated monomers or with monomers added after the free radicals have reacted with the nitroxide. can. Free radicals can be removed by any method well known in the art, such as by decomposition of azo compounds, by cleavage of alkoxy groups or by removal of H atoms from suitable hexamer or polymeric compounds, or by removing free radicals from olefins. It can be produced by addition.

Preferably, in the process of the invention, heating of the compound of formula I and the monomer is carried out in a non-polymerizable medium such as, for example, benzene, toluene, ethyl acetate.

The process of this aspect of the invention is particularly suitable for the production of oligomeric polymers and copolymers, including block and graft copolymers, and of course involving the reaction of two or more different monomers.

Thus, the polymerization process of the present invention can be performed using formula I with suitable substituents.
can be controlled by the choice of alkoxyamine, the choice of polymerization temperature, and the amount and type of monomers added at any time. For example, additional nitroxide groups of formula 5 can be added, if desired, to stabilize the growing polymer chain. Although this growth-controlled radical polymerization will proceed until the monomers present are consumed and then stop, the polymeric free radicals are in fact "living" and the polymerization continues when additional monomers capable of polymerization are added. I'll do it. This additional monomer is not necessarily the same as the previous monomer, so this growth-controlled free radical polymerization increases the flexibility and ability to produce polymers of controlled chain length and to form block and graft copolymers, for example. It has several advantages.

Furthermore, the method of the invention is applicable to a wide range of monomers. Moreover, it is now possible to easily combine short-chain oligomeric polymers from unsaturated monomers, since the length of the polymer chain depends on the monomers present during the reaction and This is because it can be controlled by the relative amounts of initiators.

In one form of polymer produced by the method of the present invention, the polymer is an oligomer having functional groups that can undergo further chemical reactions to form useful materials. The resulting polymer is shown as formula 1 and has a terminal oxyamine group at one end of the chain and an initiator residue (X) at the other end, and chemically reactive functional groups along the chain depending on the monomers used. The product of this process will thus have at least one functional group per molecule.If it is necessary to remove the oxyamine end group for technical, economic or other reasons, or may be desirable; this can be achieved by various methods to provide stable functional groups at the ends of the polymer chains. For example, reduction by well known methods, e.g. The latter can be reoxidized to nitrooxide. The oxyamine-terminated polymer can be reacted with a hydrogen donor, such as a thiol, to form a hydrogen-terminated polymer and a hydroxylamine, which can be reoxidized to nitrooxide and other free radicals If the final monomer unit is methyl methacrylate, the oxyamine forms a decomposed amine; oligomeric polymers with these unsaturated end groups have been named macromers. Macros can be further polymerized or co-incorporated via unsaturated oro groups to give polymers with side chains.

If the nitroxyterminal group is retained as part of the polymer molecule, the alkoxyamine can have other functional groups that can be used for further reaction of the oligomer. Alternatively, the X group derived from the initial free radical initiator can have a functional group.

Mixtures of monomers can be added in the polymerization stage to create random copolymers similar to those produced by conventional free radical polymerization, apart from controlled chain length.

In contrast to the problems associated with the prior art for making Zorotsk copolymers, the process of the present invention clearly creates block copolymers with as many different monomers as desired and produces block copolymers with short sequences of monomers. These would be a new class of materials with properties different from any copolymers of the monomers in question.

If desired, a block copolymer having reactive functional groups as described in 5 above can be provided.

In one embodiment of the method of the invention, "C" provides a two-step process for preparing a graft copolymer, which consists of first
In a stepwise reaction, a polymer having a pendant alkoxyamine group of general structure I is formed, and further monomers are added to the product of the first step reaction to form a graft copolymer by growth-controlled free radical polymerization. The graft copolymer can be isolated by methods well known in the art. It should be noted that this method yields a graft copolymer substantially free of homopolymers such as those having alkoxyamine groups. One way to prepare polymers is to prepare them in advance in the presence of nitroxide.
This can be accomplished by the methods described above or by reacting the polymer with free radicals capable of removing hydrogen atoms from the polymer in the presence of nitroxytide.

Preferred radicals for this purpose are 5-oxygen-centered groups such as hydroxy, 1-butoxy and benzyloxy. Depending on the temperature, the products of this reaction can be isolated for analysis or storage, or can be subjected to the next step of the reaction without isolation. In another embodiment of the process of the invention, at least one of the monomers contains two or two alkoxyamine groups, such that it is possible to form polymers containing alkoxyamine groups of the general structure of formula I. A method of producing a polymer having an alkoxyamine group is provided which comprises copolymerizing the above monomers.

The alkoxyamine can be any specified in Formula I. The grafted chains can be formed by any of the polymerization methods described herein and can themselves be homopolymers, random copolymers or block copolymers.

To aid in the understanding of this feature of the invention, the chemistry of the graft polymerization process of the invention is as follows (shown in an illustrated system diagram 1-0) The invention will now be illustrated by the following non-limiting examples: Alkoxyamines and polymer preparations were carried out in evacuated and sealed containers with degassed solutions. Degassing was performed during 6 consecutive freeze/thaw cycles.
I went to Tor. 1H NMR spectra were analyzed by Variation using deuterochloroform as the solvent (unless stated otherwise) and tetramethylsilane as the internal standard.
an EM 390 or Bruker WM 25
Recorded on a D spectrometer. HPLC&XD
U Pant 850 liquid or toge rough ult
rasphere OD8 or Zorbox ODS
Went on Qasim. GPC measurement is performed by waterssyst
using a 5-f icrostiroglu column on em.
This was done with an exclusion limit of o - i o' angstroms. 1.02 Tetrahyroalan as a bathing agent
1nI! A flow rate of /min was used and the system was calibrated with polystyrene standards. The salt and solvent were purified by standard techniques immediately before use.

What is the half-life of an alkoxyamine?
Values obtained in the presence of a 0-20 fold excess of nitrooxygen are referred to. The nitrooxytides chosen as scavengers are of course different from those resulting from the dissociation of the alkoxyamines under investigation.

The disappearance of the alkoxyamine was followed by HPLC and an internal standard was used in each case.

1.1.3. In accordance with the published procedure for the synthesis of 3-tetramethylisoindolin-2-yloxyl:1.
1.3.3-Tetraethylisoindolin-2-yloxyl (melting point 54.5-55.50)
Riffiths, Moad, Rizzard.

and soiomonl Au5t, J, Che
m, 36 3γ7° (1983). In this way, N-
Benzyl 7-talimide was converted to 2-benzyl-1,1,3,3-tetraethyl-indoline by reaction with excess ethyl Grignard, and the pencil group was converted to Pd.
, A' removed by Mizusaki decomposition and produced 1
1.3.3-Tetraethylisoindoline was oxidized to nitrooxygen with hydrogen peroxide/sodium tungstate.

1.1°3.3-tetra-n-propylisoindolin-2-yloxyl was prepared as a yellow-orange color in a similar manner using n-probyl Grignard reagent in place of ethyl Grignard r. .

Following the general strategy for the reaction of Nidrones with Grignard reagents developed for the synthesis of substituted pyrrolicin-1-yloxyls (J, F, W, Keana, 'NewA
spectra of N1troxide Cheml
Str7' + in' SpinLabel11i
ng″, L, J, Berliner ed,, A
academicPress, New York, N.
, Y, Vol 2 + 1979) 2.

6-dimethyl-1-hydroxypropylpiperidine-1
-yloxyl to 2,6-dimethyl-2゜6-di-n
-Propylpiperidin-1-yloxyl was made.

In this way, 2,6-dimether-1-hydroxypiperidine? : Oxidized with mercuric oxide to give nidrone.

This was reacted with n-propylmagnesium iodide to give 2,6-dimethyl-1-hydroxy-2-propylpiperidine, which was then oxidized with mercuric oxide and the product nidrone was converted to n-propylmagnesium iodide. Reaction with dide gave 2,6-dimethyl-2°6-dipropyl-1-hydroxygiberidine. This was oxidized with air in methanol containing a catalytic amount of cupric acetate to give the nitroxide, which was isolated by chromatography on silica gel as an orange oil.

8. By decomposition of the azo compound in the presence of nitroxide [Scheme 1] 5ci+l
e+me l Example 1 Preparation of azobisisobutyronitrile (in benzene (15d))
The degassed solution of 328fff) and 1.1.3,3-tetraethelisoindolin-2-yloxyl (500q) was heated at 70°C for 16 hours. The m solution was chromatographed on silica gel and the desired product was eluted with benzene. Crystals from methanol/water are 2-(1-
Cyano-1-methylethoxy)-1,1,3,3-tetraethylindoline (560), melting point 6 filtration 64
°; is. ”HNMRδ (CDCts): 0.7
5 (6H, t.

J-7Hz, 2XCH2CHa), 0.95
(6H, t.

J=7Hz, 2XCH2CH3), 1.75 (6
H, S +QC(CH3)2CN), 1.9-2.2
5 (8H, m, 4xcan2an, ), 6.95-7
．． 65 (4H, m, ArH).

In (solvent) with manual aging period 60° = 68 minutes (light petroleum), 66 minutes (ethyl acetate), 22 minutes (acetonitrile), 20 minutes (
dimethylformamide), 17 minutes (methanol), 1.
6 minutes (methanol:water, 9:1), 15 minutes (methanol:acetic acid, 9:1).

Example 2 Azobisisobutyronitrile (1701#) and 1°1.
3.2 mg of 3-tetra-n-zotetra-bilysoindolin-2-yloxyl (4oorn9) was dissolved into 6
Heated at 0°C for 4 hours. The title compound was provided as a solid (320rn9) on light petroleum/ben, mp 110-112<0>C. "HNMRδ (CDC13): Ll, 85 (
12H, wide t * 4 X CH2CH 2 animals 3), 1.
15-2.1 (16H, wide In + 4 X CH2C
H2CH3), 1.7 (6H.

s, QC(CH3)2CN L 6.95- 7-3
5 (4H, m.

ArH). Half-life is 60°, 261 minutes.

Example 6 Azobisisobutyronitrile (22
0da) and 4-benzoyloxy-2゜2.6.6-tet2
Degassed liquid #j with methylpiperidin-1-yloxyl (5501W) was heated at ˜72° C. for 16 hours. The bath was concentrated and the resulting solid was crystallized from methanol to yield a white prism of 230 η, mp 127.5-129°C.

"HNMRδ (CDC23): 1.3 (12H,
s, (CH3)2CNC(CH3)2), 1.75
(6H, s, QC(CH3)2CN), 2.05
(4H, m, CH2CHOCH2), 5.3 (
IH.

m, CH2CHOCH2), 7.5 (3H, m
, ArH), 8.05 (2H+m+ArH')
. At half-life 600 = 160 minutes.

Example 4 Azobisisobutyronitrile (+CN) in benzene (10 m)
200η) and 2,2,5,5-tetramenalpyrrolidin-1-yloxyl (300,1ψ). : Heated at 67°C for 18 hours.

The product was purified by column chromatography (on silica sol and petroleum ether:pe/zene (1:
1) was isolated as an oil (170 mm). “HNM
Rδ(CDCl2): 1-2 (6H, S 5N-
C(CH3)2), 1. -6(6H, s, NC(C
H3)2), 1-65(6H,s, QC(CH
3) 2CN), 1.7 (4H, s.

CH2CH2). Half-life: -280 minutes at 60°C.

Example 5 4,4'-azobis(4-
Cyano-n-pentanol) (220”S/%0.8
7 mmol) and di-t-butyl nitroxide (25
The degassed bath solution with 1.74 mmol) was incubated at 360 nm for 24 h at 20 °C in a Rayonet apparatus in a constant temperature bath.
It was irradiated with Chromatography on silica sol (using light petroleum/ethyl acetate (3N) as bathing agent) gave the title compound as a colorless oil (190~). 1HNMR
δ (CDC13): 1.2 (9H%, B,
C(CH3)5), 1.5 (9H,s, C(C
HI5)3), 1.65 (3H, s, CH3),
1.9 (4H, m.

CH2CH2), 3.7 (2H, wide t, o,), half-life = 8.5 min at 40 °C.

Example 6 2.2.6.6-Tetramethylbiperidin-1-yloxy (600 μ, 6.85 mmol) and 4 in ethyl (20Id)-2,2,6,6-titramethylbipeacetate (20Id) A degassed solution of 4'-azobis(4-cyano-n-pentanol) (500 In?, 1.98 mmol) was heated at 80'C for 2 hours.

Chromatography on silica gel using silica/ethyl acetate (1:1) as eluent gave the desired product as a colorless product (150 η, 28% yield). ”HNMR
δ(cDct3): 1.1 (9H, wide S.

3xcH,), 1.3('4H,s*2xcH,), 1
．． 5 (5H, 8), 1.7 (3H, s, CH3)
, 1.9 (4H\+ m), 3.7 (2H, wide t,
CH2CH,O), mass spectrum CI (CH4)
m/e: 269 (M[(''), 156°140
゜Example 7 Preparation of (7) Seymoptylberoxyoxidylate (95 drops) in styrene (5 ml) and 1.1.3. The degassed solution with S-tetraethylisoindolin-2-yloxyl (200In9) was heated at 50<0>C for 4 hours. After removing the evaporates under reduced pressure, the residue was dissolved in warm methanol and cooled in a refrigerator to give the title compound (245 mg) as colorless needles.
) gave a melting point of 85-86°C. 1HNMRδ (CDC
l2) : 0.25 (4H\r t + J-7H
z l' CH2CH3), IJ, 8-1.15 (9H
, m, 3XCH2CH6), 1.22 (9H, s.

QC(CH,)3), 1.3-2.8(8H, wide m,
4XCH,CH,), -e##;3.4 (I H,d
d, J = 10, 4Hz.

0CH2CH), 3.75 (I H, dd, J=
10, 4Hz, '0CH2CH), 4.75 (l/
2H, d, J = 4 Hz, 0CH2CH), 4
−85 (”/2 H, d, J = 4 Hz, O
CR, 2CH), 6.85-7.5 (9H, m,
ArH).

Example B 2-(2-t-Butoxy-1-methyl-1-phenylethoxy)-1,1,3,3-tetraethyl 1.1.3°6-tetraethyliso in α-methylstyrene (5M) Indolin-2-yloxyl (5609) and di-t
-Butylperoxyoxidry) (240+111&)
Tokara title compound (520 yen); melting point 87-89°C
was recrystallized from methanol. “HNJaδ(C
DCl2): 0.4-1.05 (12H+m+4
XCH2CH3), 1.1 (9H,s.

(C'H3)3CO), 1.4-2.5 (8H, wide m
+ 4 × CH2CH3), Yaw = 1.75 (3H
, s, an3c'o), 3.4 (IH.

d, J-9Hz, 0CH2), 3-6(, IH
,d,,r=9Hz,0CH2),6.8-
7-6 (9H, m, ArH).

Half-life at 60'C = 75 minutes.

Example 9 1,1,3°6-tetraethylisoindolin-2-yloxyl (28 ml) in 5 ml of 1,1,3,3-tetraethylisoisoimethacrylonitrile
I & ) and G also monobutyl peroxyoxy → r rate (
C1B
This was extracted as an oil ('1) by preparative reverse phase HPLC using a column.
801ψ).

Magnetic spectrum = MH + calculated value, 388.301, measured value 687.3 DI. “HNMRδ (CDCl2)
: [1,7(6H~, t, J=7 Hz,
2X CH2CH3), 11.95 (6H.

t + J-7Hz l2X CH2CH3), 1
．． 25 (9H.

s r (CH3)3CO), 1.68 (3H, s
, CH3CCN), 2.0 (8H, IIl, 4X
CH2CH3), 3.4 (1a, d.

J-9Hz, 0CR2C), 3.75 (IH, d,
r=5+Hz, 0cI(,c), 7-1(4H
, m, ArH). Half-life at 60C = 55 minutes.

Implementation f9ui.

2-(2-t-butoxy-1-methoxycarbonylation 1
The title compound was prepared as in 1Il19, but methacrylonitrile was replaced with methyl methacrylate (5M). This was analyzed by HPLC using a C18 column and 84% ethanol/16 water as the eluent.
It was single @ed as 85+11&).

Mass vector: MH+#t:]+straight, 42L1.3
11, 1 shift 4 2 0.3 0 9゜ 1HN
MRδ (CDC73): 0.7 (6H\, t
, J”' 6I4Z, 2X CH2CH3),
0.9 (6H.

dt, J”' F3.2Hz, 2X CH2CH
3), 1. ．． 22 C9H.

s r OC(CH3,)3 ), 1.62 (3H,
, s, CH2CCH3), 1.4-2.4 (3H
, m, 4 x CH2CH3), 6.45 (I H
, d, J = 9 Hz, 0CH2C,), 3
．． 72 (1, H.

d, J-9Hz, 0CH2C), 3.8 (6H
,s.

0CR3), 7-2 (5H, m, ArH) o half-life, 60°C = 126 min.

Example 11 1-(2-t, -cytoxy-1-methyl-1-7e α-
A degassed solution of 2,6-dimethyl-2,6-di-n-propylpiperidin-1-yloxy (80 rng) and monobutyl peroxyoxyoxylate (40 rng) in methylsteric acid (2 ml). 1.25 at 50℃
heated for an hour. Chromatography on silica gel after evaporation of the volatiles gave the title compound (5(lly)) as an oil (bathed with light petroleum/benzene 4=1)."HNMRδ(CDC4s)' 0.2- 1-9
(26H1m), 1. tJ 8 (SoH~+s
p QC(CHs)3), 1.8 (3H,s,P
hCCH3), 3.35 (1H, d, J = 9
Hz, 0CH2C), 6.68(1'H, d,
j = 9Hz, 0CR2C), 7.4 (5H.

m, ArH). Half-life: 60” 210 minutes at O.

Example 12 1-(2-t,-butoxy-1-phenylethoxy)
-2,6-dimethyl-2.6-n-propylbipe The title compound was prepared as in Example 11 except that α-methylstyrene was replaced with styrene (27117) and isolated as an oil in the same manner at °C. did.

"H, NMR δ (CDC73): 0.2-1.8 (
26H, m), 1.0 (9H, s, QC(CH3
) p ), 3.28 (I H, m.

OCH, CH), 3.78 (I H, m, 0CH2
CH)s7-3 (5H1 wides, ArH). Half-life of 80° = 400 minutes.

Example 16 Synthesis of monobutyl nitroxide (200 mm) and di-t-butyl peroxyoxalate (BOrn The degassed solution was heated at 45 °C for 1 h. The volatiles were evaporated and the residue was chromatographed on silica gel (pumice/benzene 4:
1) gave the title compound as an oil (2301#). 1HNMRδ (C'DC23): 0.95 (
9H, S, NC(CH3)5), 1.05(SoH*
s + NC(CH3)5), 1-6 (9H+
S.

QC(CH3)3), 1.75 (3H,s, C4
(2CCH3), 3.4 (I H, d, J = 8H
z, 0CH2), 3.7 CI H.

a, J=13Hz, 0CH2), 7.4(5H, m,
ArH).

Half-life at 40°C = 18 minutes.

Example 14 α-methylstyrene to acrylonitrile (5M)? Instead, prepare the title compound as in Example 16. I made I. The oil (18
It was isolated at 0°C.

Phase NMRδ (CDCA3): 1.19 (9H, s
, QC(CH3)3), 1.24 (9Hs s
, NC(CH3)5), 1.27 (9H.

s + NC(CH3)5), 3.6(2H, d,
J=7Hz.

0CH2CH), 4.7 (i H, t, J = 7
Hz, 0CH2CH).

Half-life: 2105 minutes at 90°C.

Example 15n A degassed bath of di-1-butyl nitroxide (400 q) and di-1-butyl peroxy oxidate (234/ng) in styrene (5/d) was heated at 5[]"O for 2 hours. The title compound was isolated as an oil (560 mm) by chromatography on silica gel using 1:1 pumice/benzene as eluent (which solidified on storage).

"HNMRδ (CDC7,): 0.8-1.6 (
18H, wide m.

2 X NC(CH3)5), 1.08 (9H, s
, QC(CH3)3), 6.52 (i H, dd
'+J-11,7Hz, 0CH2CH), 6.9
5 (I H, dd, J, == 11.5 Hz
, 0CH2CH), 4.84 (''/2 H, d,
J = 6 Hz, 0cH2CH), 4.9
(”/2 H, cl, J = 6 H2,0CH2C
H), 7.25 (5Hrm, ArH). Half-life 8
= 70 min at 0°C; 222 min at 90°C.

Example 16 Grafting 0 octoid (product (16)
) ×
00), di-t-butyl peroxyoxalate (5
8η)'d and di-t-butylnitrooxibide (12
The degassed solution of 0I) was heated at 50°C for 2 hours. Reaction Mixture B was slowly added to 75ml of acetone C while stirring to give the polycitadiene-containing grafted nitroxide (0,55,9). 1HNMR Aδ
The signal at 1.2 confirmed the presence of nitrooxytide grafted at a ratio of 27 butadiene units to 1 nitrooxytide. Further precipitation in acetone did not change the composition of the polymer.

Example 17 Grafting of xyl (Product (17)) Poly(imbutyl methacrylate), (0,5,9) and 1.1,3°6-titramethylisoinr-2 in tetrachloroethylene (3 ml) -ylonisyl) (210rn
g) and di-t-butyl peroxide) (120
The degassed solution with η) was heated at 50° C. for 6 hours. The reaction mixture was stirred in methanol (25IrLl) to give the grafted nitroxide (0,64) containing poly(imbutyl methacrylate). 6.9
−7.3, the grafted nitroxide is 15
It was confirmed that the inzotyl methacrylate unit was present in a ratio of one nitroxide unit to one nitroxide unit. Although it was roughly purified, the composition of the polymer did not change.

Example 18 4-cyano-4-(2,2,6,6-tetramethylpiperidine-1-oxy)-pentyl methacrylate (18
) Preparation of methacryloyl chloride (1
74 rvs 1.7 mmol) to triethylamine (3
1-(1-cyano-4-hydroxy-1-methylcytoxy)-2,26,6-titramethylbiperidine (Example 6) in diethyl ether (107d) containing After stirring the reaction for 1 hour at ambient temperature, trimethylamine/(2 ml) and water (10 TrLl) were added and stirred for a further 1 hour. The layers were washed with saturated picarbonate, water, brine, dried over 4 gnesium sulfate and concentrated. Chromatography on silica del and chloromethane elution gave the title compound as a colorless compound (1.32 my, 70% yield). lHNMRδ (cDcz, ): 1.1 (9H,
s, ), 1.3 (4H, S), 1.5 (5H, wide s)
, 1.95 (7H, m), 4-2 (2H, m, 0
CH2), 5.5 (1a r m + olefin properties 2)
, 6.1 (IH, broad S, olefinic CH2). Mass spectrum CI (CH,) m/e: 337 (MI, 15
6. ．． 140° Example 19 Acryloyl chloride (540'll &, 5.97 mmol) in diethyl ether (15#LA') in diethyl ether (20d) containing trimethyl (1,22,9,12,4 mmol) 1-(1-cyano-)
4-hydroxy-1-methylbutoxy)-2,2,6,
Add slowly to the cooled solution of 6-titramethylbiperisone (5661#, 1.98 mmol) (Example 6).

Trimethylamine (5M) after stirring for 40 minutes at room temperature.
and water (5M) and stirred for 60 minutes. The ether layer was separated and washed with water, saturated picarbonate solution, brine, dried over magnesium sulfate and concentrated. Chromatography using silica del and dichloromethane as eluent gave a colorless product <416 m9.65
% yield). “HNMRδ (CDCl2)
'1.11 (6H, S), 1-15 (3H, s),
1.51 (6H, m), 1.67 (3H, s, C
H-C-CH,), 2.02 (4H, m), 4-2
3 (2H, m, CH2-0).

5-68-6.54 (3H, m, olefin H).

Quality g spectrum ('I(CH4) m/e: 32
Ethyl acetate (7 m
6) in the title alkoxyamine (5001!, 1.49
mmol) and styrene (1.6 g, 15.4 mmol)
The degassed solution was heated at 65° C. for 2 hours.

The product is precipitated from methanol to give a white powder of 870 kg. GPC: Mn=3003, Mw/M
n"" 1.5, "HNMRδ (CDCl2):
0.7-2.5 (aliphatic H), 6.2 (broad S,
0Cf(2), 6.3-7-4 (ArH).

It was determined that 1 alkoxyamine for every 8 styryl units was present in the copolymer from the total values obtained from HNMR. This means that on average the C4 alkoxyamine component was incorporated into one chain. Example 21 Sea 1-glythyl peroxyoxidrate (200IV,
Ethyl acetate (15 rrd
l) Titled alkoxyamide/(500 Y, 1.4
5'mmol) and methyl methacrylate (1,5#,
The degassed solution with 15.0 mmol) was heated at 35°C for 20 hours. The product is a white powder (1,6
g) Precipitated at ℃. GPC: Mn=4325,
Mw/dest = 1.6゜”HNMRδCCDC1,):
0.5-2.0 (fat + 17j group H) 3.4-3.9
(Oken 3).

``From the HNMR overall data and the GPC determined molecular weight, it was estimated that 6 alkoxyamine units were incorporated per chain (ratio of 1 alkoxyamine per 7 methacrylic methyl units).

Example 22 Rubiberidin-1-oxy)pentyl acrylic acid t
-Butylberoxyoxyoxidinate (20,11Iv) in ethyl acetate (5me) containing the title alkoxyamine (100'll &, 0.31 mmol) and acrylated methyl (270η, 3.13 mmol). The degassed solution was heated at 65'G for 18 hours. The product was isolated as a gum (
The product was given as 13υtp). 1HNMRδ
CcDct, 3): 1.12-2.3 (aliphatic H)
, 3.66 (■ and 3), 4.10 (Mrs. 20).

GPC: Mn = 3756, M, /M, = 2.4° It was concluded from the overall IHNMR and GPC data that approximately 4 alkoxyamine units were incorporated into one chain (ratio of 1 alkoxyamine per 10 methyl acrylate components). .

Preparation of homopolymers and random copolymers Example 2
6 A, (n=1). 2-(1-cyano-1-methylethoxy)-1,1,3,6-tetraethylisoindoly/(62) in benzene (91117) and acrylbamethyl (1) and 1.1.3. A degassed solution of 3-tetraethelisoindolin-2-yloxyl (1η) was heated at 80°C for 6 hours. Removal of the volatiles gave a colorless gum (90my), which was identified by NMR and HPLC as the title compound n-1 and a small amount. It was shown that the title compound (n=1) is composed of n:==2 and 3.
65rn&, 82%) by chromatography on silica using benzene and a benzene/ethyl acetate mixture as the M eluent. IH4R(9
0MHz) δ: 0.4-1.1 (12H, m.

4 X CH2CH3), 1.42 and 1-48 (
6H, s*C(CH3)20N), 1.5-2-4
('8 Z (2m, CH2CH3), 2.08 (
2H, a, J=78Z, Csu〉CM-o), 2.8
0 (3HIS, C0CH5), 4.60 (IH,
t,, J=7 Hz, CH2C'H-0), 6.9
−7.6 (4H, m, ArH).

s, (n=7). 2 in methyl acrylate (101d)
-(1-cyano-1-methylethoxy)-1゜1.3.
3-te) Laeter isointari: y (62,5σl)
and 1,1,3,3-tetraethelisoin 1-2-
A degassed solution of yloxyl (0,5η) was prepared at 80°C for 1
．． Heated for 5 hours. One part of both solutions (5mA) was drawn out and used for the bottom 0 part.The remaining part (5rnl)
Removal of volatiles from NM gives a colorless gum (95η)
RK showed the title structure, where measurements of peak intensities gave an average of n = 7. ”HNMR (90M
[几) δ: 0.3-1.2 (CH3-CH2), 1.
65 and 1.40 (ON-C-(cf(,,)2),
1-2-3.0 (CH2-CH), 3.7 (-0
CHs), 2) were heated at 100°C for 4 hours. Removal of volatiles gave a colorless gum (165 η) and NMR showed that the title oligomer was composed of an average of n-14. 1H NMR of this oligomer differed from that of part B only in the peak intensity of the terminal group.

D, (n=70), a solution of the oligomer (80 In?) from part B in methyl acrylate (5 M) for 12
Heated at 0°C for 1.5 hours. Removal of volatiles gave a colorless gum (0,57,9), which was shown to consist of the indicated oligomer (n~70 average) by 1H NMR.GPC': nn=670[]sMw/
Mn=1.82゜Example 24 A, (n=11), 2-(1-cyano-1-methylethoxy)-1゜1.3 in acrylic methyl 5-methyl (5M)
, 3-tetra-zorobylisoindoline and 1.1.
3.3-tetra-n-delobylisoy F IJ 7
The degassed solution with -2-yloxy k (0,25IQ ) was heated at 80 °C for 1 h. A sample (approximately 1 tnlt) of the reaction mixture was collected and shown to contain the title oligomer (n=11 on average) by HNMR fractional analysis.

B, (n=i6L) 10% of the residual reaction mixture from part A
Heated at 0°C for 2 hours at which point a sample (approximately 1 kg) was removed and analyzed by ↓HNMR spectroscopy to identify the title oligomer (
On average, n=16).

c, (n = = 21 L The remaining reaction mixture from part B was heated at 100 °C for an additional 4 h. Removal of volatiles gave a colorless gum (14 o η). =21)."HNMR (90MI(z)δ:0.7-1.
0 (CH2CI(2CH3), 1.61 and 1.3
8 (C(CH3)2C'N, - doublet), 3.7 (CO
OCH3), 4.1-4.6 (CH2C'H-0),
6.9-7.3 (ArH).

Example 25 1-(1-cyano-1 in methyl acrylate (51d)
-Methyl ethoxy)-2,2,6,6-tetramethylbiperadiy (45 mg) degassed layer liquid? 1 at 100℃
Heating for an hour gave the title oligomer (n-4 on average). 120'C! When heating is continued for 5 hours at
= increased to 5. Upon heating at roughly 140"C for 2 hours, the chain length increased to an average of n = 22 as determined by NMR fractional analysis. When a portion of the reaction mixture (6M) was added to light oil (30mA) a colorless product ( 270 yen).IHNM
R (90MHz) δ: CJ, 9-1.25CH-C-C
H3), 1.31 and 1.58 (C(CH3)2O
N), Ro-7 (COOCH3), 4.1-4.4 (
CH-0-N).

Example 26 ti-(2-t-
Butoxy-1-phenylethoxy)-N,N-di-(-butoxy-1-phenylethoxy)-N-di-(-gylamine (52 ql) was added to the degassed U solution for 10 minutes.
Heated for 0.5 h at 0"C. Removal of volatiles gave a colorless gum (υ, 42.?)Y, which was shown to have a traverse of the title oligomer by NMR with an average of n-25
Met. GPC: Mn=25L]0゜Mw/Mn=
1, 7°IHNMR (250MHz) δ: 1.1
0S and 1.11 (sharp number 1, 0-1-butyl),
1.15 and 1.23 (extended single term, N-t-butyl), 3-68 (C00CH3), 7.1-7.
55 (ArH).

Example 27 A, (n=4.5) N- in styrene (3mi)
(2-t-butoxy-1-phenylethoxy)-N.

N-genie butylamine (3UI#) and Genie butyl nitro oxide C0.5m? The degassed liquid was heated at 100°C for 1 hour. Removal of the volatiles gave a colorless gum C76tny) which was shown by NMR to consist of the title oligomer (average n=4.5).

B, (n=12) The product from the capital of A and the 1-butyronitroxy group (0,5η) are combined with styrene C5m1)
The mixture was degassed and heated for an additional hour at 100"C. After removing the volatiles, the title oligomer (160111&
) occurred on average n=12. ”HNMR(9Q M[(
z) δ: 0.7-1.3 (0-t, -butyl and I4-1-buteryl), 3.1-3.4 (CH2
-'O), 6, Sea-a, 2 (ON-ON), 6
．． 5-7.5 (ArH).

Example 28 A degassed liquor of N-(2-tert-butoxy-1-phenylethoxy)-N,N-di-1-butylamine (32 ory) in anhydrous vinegar-modified vinyl (3 nte) was added to 12 U''
The mixture was heated at C for 1 hour. After removal of the volatiles, a colorless gum (55 Iψ) was shown to be formed by NMH with an average n=2.5 of the labeled oligomer 7). “HNM
R (90MHz) δ: o, 7-1.4 <υ-1-
butyl and Nt-butyl), 1.7-2.1 (C
H2 and CH3COO), 6.2 = 3.5 (C
H20), 4.6-5. i (CH-OAc), 6
．． 1-6.6(0-CH-0'), 7.2+Ar)1)
.

Row 29 2-(1-cyano-) in ethyl acrylate (10d)
1-methylethoxy)-1,1,3,3-tetraethylisoindoline (66Ing) and 1,1゜6.6-tetraethylisoinrlin-2-yloxyl (0,5i
The degassed m solution with w) was heated at 80'C for 2 hours, followed by 0.5 hour at 120''O.

Volatiles removed 1- and average n-11 title oligomer
(290 my) was obtained. ”HNMR (90MHz)
δ: 0.4-1-1 (C-CH2CH3), 1.1
-1-4 (COOC'H2CH3-N-■■■-I-
-1-■-1- and C-CH5), 1.4-2.5 (CH2-CH
), 4.1 (COOCH2CH3), 6.9-7.3-
(ArH).

Example 30 N-(2-t-butoxy-1-phenylethoxy)-N in styrene (3 ml) and methyl acrylic (3 ml)
A degassed solution of N-geniebutylamine (61 chloride and soybutyl nitroxychloride I'CI), 5η) was heated at 100° C. for 1 hour. “HNMR (90 Ml) of the product (140 I Da) obtained upon evaporation of the volatiles.
The spectrum is based on the C-1-butylaminoxy group (CH3
, δQ, 8-1.3 ) on average -[5,5 styrene units (Ar, 66.4-7.4
) and 4.6 methyl acrylate units (COOCH,,
It was shown that it is a random copolymer with 3.1-'3.7). penulti-
mate) groups are both styryl (Ph-CH-OH,
δ6.9-4.2 ) and acrylate (CH300
It consisted of C-CH-ON, δ4.6-4.7) units.

Example 61 Methyl methacrylate (101M) and styrene (0.5M
A degassed solution of N(2-t,-cytoxy-1-methyl-1-phenylethoxy)-N,N-y-t,-1 thylamine (30 rng) in 1) was heated at 60 °C for 0.75 h. Heated. Removal of volatiles gives a colorless gum (105η
) was obtained, and its "HNMR was determined by the title oligomer (n=10
) has a structure of about 20 with an olefin end group.
It was impure with % oligomer. Termination of the growing poly(methyl methacrylate) group in this case can be accomplished by disproportionation with nitroxide to give an olefinic end group (see Working #J Examples 66 and 64) or by addition of styrene units followed by nitroxide and cadel. It can also be obtained by giving the title oligomer. Since the latter alkoxyamine terminal group does not dissociate into radicals at 60° C., the growth reaction is further reversed.

"HNMR(9[3M[(z)6:L]-4-
1,6 (C-CH3), 1.7-2.2 (stem CH2)
, 2.8-6.3. (0-C) following i3Ph),
3.6 (0-C'H3), 4.6-4.8 (Ph bilotq), 5.45 and 6.2 (c = CH2)
, 7.5 (ArH).

Example 62 Cooligomer of methyl methacrylate and ethyl acrylate Ethyl acrylate (4 hemp) and methyl methacrylate (1 m
13) N-(2-t,-butoxy-1-phenylethoxy)-N,N-dit,-phthylamine (64■)
The degassed liquid was heated at 100° C. for 1 hour. Evaporation of the volatiles gave a colorless solution (0,559). The HNMR of a random co-oligomer shows an average of 15 acrylic acid ethyl units per chain (Coo 2CH3, δ3.8-4.
3) and methyl dimethacrylate unit (COOCH3)
, δ6.6). Methyl range (δ0.7-
The number of protons in 1.4) indicates the presence of a di-1-dithylaminoxy end group, which may be attached to the Q ethyl acrylate unit; = 26001 MW/rice = 1.7. > Ribopolymerization: When α-methyl substituent monomers, e.g. methyl methacrylate and methacrylateryl, are polymerized using alkoxyamines as initiators, the termination of the growing chain is hydrogen from the α-methyl substituent to the nitrooxy group. Atom migration occurs to produce polymers with olefinic end groups (macromers) and corresponding xylamines.

Example 66 (61) N-(2-
1-butoxy-1-methyl-1-phenylethoxy)-
The N,N-di-1-butylamide/(34rn9) degassed solution rffl' was heated at 50° C. for 0.5 h.

Removal of the volatiles gave a colorless gum (32D m?) which was shown to consist of the title oligomer by NMR, where n=27 on average. “HNMR(9[JM
Hz) δ: 3.65 (C-COOCH3), 5-
7 (CH2=C-COO4,), 5.45 and 6.
2 (C=CH2), 7.25 (8rH).

Example 64 Δ, (n=30) 1 in methyl methacrylate (4 ml)
-(1-cyano-1-methylethoxy)-4-oxo-
2,2,6,6-tetramethylbiperidine (50 rng
) was heated at 80°C for 8 hours. Evaporation of the volatiles transforms the title oligomer into a colorless rubber (0,
6,9> approximately 6 per chain by NMR.
It was concluded that it contained 0 monomer units. ”HNMR
QMHz) δ: 1.35 (ON-C-(CH3
)2), 3.65 (C-COOCH3), 3.7 (
CH2=C-COOCH,), 5.45 and 6.2
(C””CH2). GPC: Mn=520 tl,
MW/Mn = 1.15゜1-Hydroxy-4-oxo-2,2,6,6-tetramethylpericin was isolated by extraction of the title oligomer with light petroleum 1- and by comparison with the authentic sample. confirmed.

B, (n=230), methyl methacrylate (10ml
) in 2-(1-cyano-1-methylethoxy)-1,
1,3,3-tetraethylindoline (64rn9
) and 1.1.3.3-tetraethylisoin group phosphorus-2
-yloxyl (0,25' degassed solution fzr
: Heated at 80°C for 2 hours. Removal of volatiles gave the title polymer (2.1 g), which had a ``HNMR'' of poly(methyl methacrylate) with olefinic protons clearly visible at δ 5.45 and 6.2.GPC:
M. =22700. M,,/M.

= 1.45°C1 (n = = 50-60), repeat the above experiment using a larger amount of nitro oxytide (5oy) and 8
Heating at 0°C was increased to 15 hours to give 0.6g of polymer. In this case the terminal olefinic protons were visible in HNMR (65, 45 and 6.2) and from these it was determined that the length of the polymer was 50-60 units. Subsequent oxidation (in air) to the corresponding nitro oxtide then gave an almost quantitative yield of 2-hydroxy-1,1°3.3-tetraethylisoindoline as determined by HPLG and UV spectroscopy.

Example 65 2-(1-cyano- in methacrylonitrile (10M))
1-methylethoxy)-1,1,3,3-tetraethylisoindoline (62rn9) and 1゜1.3.3-tetraethylisoindolin-2-yloxol (0,5'
The glassy residue (200 m9) was extracted with Y benzene and left in the air overnight after being exposed to air overnight.
-tetraethelisoindolin-2-yloxyl. 1H NMR (9Q MH
z, d6-acetone) converts the olefin proton into 66
．． 17 and 6.28 whose intensities averaged approximately 30 monomer units per chain.

The following implementation shows one of the alkoxyamine-initiated polymers.
provides further evidence for the "living" nature.

Example 36 (34) Methyl acrylate oligomer (160') made in Example 26 in ethyl acrylate (31 nIV) Both degassed solutions were heated at 1000 mJ for 0.5 h.

Colorless gum (285111&) obtained by evaporation of volatiles
+7) 'H NMR analysis showed that an average of 19 methyl acrylate units per chain were added to the starting oligo (methyl acrylate). "HNMR (2501 visit 2) δ: 1.1[] and 1.11 (sharp signal, 0-nibutyl), 1.3 (one N-nibutyl, others disappear), 1-2-1.3 (0-CH24.)
, 3.68 (coocH3), 4.0-4.2 (0
-CH2CH3), 7. i-7,35 (ArH). ap
c: M, = 4300 (~7M.

=1.7). The expected increase in molecular weight was confirmed.

Example 67 Preparation of Tsuku (65) Oligomer prepared in Example 26 (100 rny
) ty) Suy-v y (5rrrl) in the middle! i'a: Heated at 100"C for 6 hours. At the start of the reaction and after 6 hours of heating, 1-butyl nitroxytide (0,5+w) was added to generate heat of styrene. Volatile matter. Removal of the compound gave the original AB block co-oligomer. HPLC fractionation, along with HNMR analysis, demonstrated that the stene unit was attached to the starting methyl acrylate oligomer. "HNMR (90MHz) δ: 0.
7-1.3 (C-CH3), 1.3-2.6 (C
'H, -CH), 3.3-3.55 (COOCH3
Next to Ar), 3.65 (COOCH3), 6.7-
7.4 (Arc).

Example 6B A degassed solution of the ethyl acrylate oligomer of Example IMJ29 (200 ml) in methyl acrylate (10 ml) was heated at 120° C. for 1 hour. The colorless gum (4601ψ) obtained upon removal of volatiles was determined by NMR to have a structure (
36) was shown to consist of the EA-MA jiglock. "HNMR (90MHz) δ: 0.4-1.1 (
C-CH2-concave 3), 1-1-1-4 (COOCH
2 sisters.

and C'-C'H,), 1.4-2.5 (CH2
-C,H), 3.65 (COOCH3) X 4. i
(COOCH2CH3), 6.9-7.3 (8rH).

Example 39 Lycopolymer~/Kidney Example 36 NoyhA-EA block (80!n9) and Sheeny butyl nitroxide (0,025'W')
A degassed solution of methyl methacrylate C2ml) was heated at 100° C. for 0.5 h. 1H NMR of the product (220rn9) obtained after evaporation of volatiles &1
It was shown that an average of approximately 60 methyl methacrylate units per chain were added to the MA-EA diblock to give the triblock of structure 4 (37).

"HNMR (25'OMHz) δ: 1.10 and 1
．． 11(O-1-butyl), 3.6 [1(C0 of MA
0CH3), 3.68 (MA (1) C00CR3
), 4.0-4.2 (0-C'H3CH3), 7.1
−7.35 (ArH). Starting Material (7) The Nt-Seal signal was no longer present. opa: Mn
= 10500 (M1v/Mn=2.6) Expected increase in H length) JD'rr, Knee L.

Preparation of graft copolymer Example 40 Tetrachloroethylene (5M) and methyl methacrylate L/-
) (2d) in polybutadiene-containing grafted genie butyl nitroxide (0,1,9) (Example 16
The degassed solution of ) was heated at 95° C. for 15 hours. The reaction mixture was added slowly to stirring acetate (20 ml) to give the title graft copolymer. δ3.65 (-
0CH3) and 1.0-2.4(CH2-CH)
The HNMR signal is 1 methyl methacrylate unit versus 6
The presence of methyl acrylate grafted onto polybutadiene in the proportion of putazoene units [62,1(CH2-CH2
), 5.4 (CH=CH)] was confirmed. δ1.2
The lHNMR signal in Y indicates that the di-1-butylaminoxy function remains bonded to the methyl acrylate chain.
I kept 1g.

Example 41 Preparation of monoethyl acrylate) Grafted 111 in ethyl acrylate (5 ml)
．． 3.3-Tetramethylisoinr/-2-yloxyl(0,29) (Real 7 [J'i117) A degassed solution of Y-containing poly(isobutyl methacrylate) was heated at 150°C for 2 hours. . The reaction mixture was added to methanol to precipitate the polymer. 1H NMR shows isobutyl methacrylate (63,7) versus ethyl acrylate (
The ratio of δ4.1) was shown to be '&1.3:1, while one word from the indolinoxy function was δ6.9-7.3.
appeared on.

Example 42 A degassed solution of the copolymer (12 η) from Example 20 in methyl methacrylate (12 ml) was added to 100%
The product was isolated by precipitation from methanol, which gave a white powder (?8+ny).

”HNIJiRδ(cDcz3) 20.7-1.6(
Aliphatic H), 5.2 (OCH2), 3.7 (OCH
3-crafted methyl acrylate), 6.3-7
．． 3 (ArH). ``From HNMR, it was inferred that 1-alkoxyamine 3-methyl acrylate was grafted onto the copolymer.

The grafted polymer (32') from Part A was dissolved in methyl acrylate (37d), degassed and
Heated at 0°C for 2 hours. The product was 429 white powder. Analysis of the product using acetonitrile with H, P, L, C, (reversed phase): TetrahyP Lofura 7C robust A as solvent: 90% CH3CN 5 min, 90%-5
0% CH30N/15 minutes) is the absence of methyl acrylate homopolymer! ' Show L. 'HNMR
J (CDCl2): 0.7-1.6 (aliphatic H)
, :6.7 (0CR3, from grafted methyl methacrylate), 6-3-7-6 (ArH) o "H
It was calculated that there were 18 methyl acrylate units present in the ring structure of the NMR spectrum.

Example 43 A degassed solution of the copolymer (C96'IQ) from Example 20 in methyl methacrylate (2,IJ/12'i-1 mmol) was heated at 100'C for 1 hour.

The monomer was removed under reduced pressure 1″ and a glassy solid (160
m9) f occurred. ”HNMRδ (CDC23):
0.9-1.9 (aliphatic H), 3.2 (CH20)
, 3.4-3.7 (4, 30° grafted methyl methacrylate to C6,6-7,1(ArH)."HN
It was calculated from the total MR that 6-7 methyl methacrylate units were gelasted for each alkoxyamine.

Example 44 Copolymer from Example 21 (100%') 'a' A solution dissolved in styrene (2 ml) and degassed was
Heated at 0°C for 4 hours. The product was isolated by chromatography using silica gel and Y/K/ethyl acetate (1:1) as eluent. This gave example homopolymer-free product '#J as a white powder (180 drops). ↓HNMRδ (CDCl2): 0.9
-2.0 (aliphatic H), 3.6 (from OCH3° trunk methyl methacrylate), 6-6-7.3 (ArH
・Grafted methyl/from). ``From the HNMR total it was calculated that 12 methyl units were incorporated per valley alkoxyamine.

(42), R''=CH3, R22H, R'=Ph(43
), R”<H3+ R2CH3,R”=C02CH3
(44L R” size a,, R””H, R3=C02C
H3 (45), R1=H, R2 Soft skin R+3=Ph Example 45 Example 21 Poly(methyl methacrylate-coalkoxyamine) (100'v) The gassed solution was heated under pressure at 100-0 L for 5 hours. Removal of the monomer under reduced pressure yielded a white powder (284111&)'a'.

"HNMRδ (cDct3): 0.7-2.1 (
Aliphatic H), 3.6 (OCH3). The amount of methyl methacrylate grafted was calculated from the weight of the product since HNMR was not useful for this purpose. suggested that.

Example 46 The poly(methylmethacrylate-coalkoxyamine)lamythyl acrylate (21 nl) from Example 21 was applied and the degassed solution was heated at 100° C. for 2 hours. When the monomer was removed under reduced pressure, a white powder (142η
) was obtained. The grafted methyl acrylate was calculated as in Example 10 and found to have 6 methyl acrylate units attached to the valley alkoxyamine.

"HNMRδ (CDCA3): 0.6-2.2 (
Aliphatic H), 3.6 (from OCH3, methyl methacrylate), 3.7 (from OCH3, methyl acrylate)
.

Example 47 Preparation of poly(methyl acrylate nyalkoxyamine) from Example 22 (87,5 ml?) of methylene (2,3
g) and degassed solution at 100'C for 2 hours. The product was precipitated from methanol and chromatographed on a silica gel, using penzetrium to remove the styrene homopolymer and then using ethyl acetate to collect the product (50 mg). IHN
MRδ (CDC23): 0.9-2-3 (IJ1
u family H), 3.6 (0CR3mefh l takujJL
'-from the trunk), 6.5-7.0 (from ArH-grafted styrene). ``From the overall HNMR results, it was calculated that 2-6 styrene units were grafted onto the Tani alkoxyamine.

Reaction of aminoxy-terminated group Example 48 Aminoxy-terminated methyl acrylate oligomer (100Tn9) and zinc dust (0.2 g) of Example 23B part
was added to the acetic acid, which was heated to reflux for 2 hours and saturated with zinc dust a further 6 times (6 times 0.1.9) during the course of the reaction. The residue obtained after filtration and removal of volatiles was dissolved in ethyl acetate and extracted with dilute hydrochloric acid. 1.1.3.3-tetraethylisoindoline was recovered from the acidic layer by causticization and extraction in near quantitative yield. When the ethyl acetate solution is evaporated, hydroxy-terminated oligomers (
Scheme 6) is given, where the "HMNR signal of No-CH-COOCH3 at 3 in 64.2-4.6 is δ4.7
−6.1, which is replaced by the signal in H
O- is attributed to -COOCH3 group.

Example 49 N-(2-t,-butoxy-1-phenylethoxy)-N,N-di-1\zoterami7C66m? of Example 15?
) to ethanethiol (11nl)? :E Toguchi And the degassed solution? Heated at 80°C for 16 hours.

HNMR analysis of the residue obtained by removing excess thiol was 1.
-Niebutoxy-2-phenylethane, N.

N-c-1-butylhydroxylamine? and diethylditylhyde. 1-1-Butoxy-2-phenylethane was isolated by chromatography on silica del in 80% yield.

'HNMR (90MHz), +5 (CCV,):
1.18 (9H.

S, O-t,,-butyl L 2.8 (2H, t
, aH2Ar), 3.5(2H,t,CH20),
7.2 (5H, Sl 8rH).

Example 50 H-terminated methyl methacrylate oligomer of structure (46) Example 23 Aminoxy-terminated methyl acrylate oligomer of C' portion (100%') was dissolved in benzene (5M) and the degassed solution was heated at 100° C. for 16 hours. Heated. Concentration of the reaction mixture and dilution with light petroleum gave a gum whose signal at 1HNla & 1.2 and 6.8-7
．． 4) showed the absence of. By analogy with the examples, the product is believed to have structure (46).

Agent: Akira Asamura Continuation of page 1 Priority claim [Phase] 198'R, July 11 [Phase] Australia 0198 tsubo July 11 [Phase] Australia [Phase] February 10, 198 [Phase] Australia @ Inventor Ejio Rizardo Australia @ Inventor Paul Cascioli Australia (AU) [Share] PGO 224/83 Australia (AU) [Share] PGO 225/83 Australia (AU) ■PG 3578/84 Are Avenue, Wheelers Hill, Victoria, Tralia 26 Masonry St., Reservoir, Victoria, Tralia
50 Procedural amendment (,8) September 72, 1980 Commissioner of the Patent Office 1, Indication of the case 1982 Patent Application No. 144097 2, Name of the invention Compound for producing polymers 3, Person making the amendment Related: Patent Fl applicant 4, agent 1936/1985 Law specification officer's engraving (no change in content) Procedural amendment October 1980 q' Mouth Mr. Commissioner of the Patent Office 1, case indication 111A Japanese 59 year 3 copy Application No. 144097 2, Name of the invention Compound for producing polymers 3, Party making the amendment 1! Relationship with 1- Patent 3T applicant 4, agent Month/Day 6, 1939, Number of inventions increased by amendment 7 , Target of amendment - (1) The chemical formula on page 78 of the specification is corrected as follows.

? ” χ +

Claims (1)

[Scope of Claims] (1) Compounds suitable for use in the process for producing polymers, especially oligomers, by free radical polymerization of suitable unsaturated super-compounds, wherein the compound has the formula (I): or a group having at least one carbon atom, and the radical X° is such a group that is capable of polymerizing unsaturation by free, radical polymerization, and the radical functionality is such that the carbon atom or identical or different straight or branched chains of sufficient chain length to provide steric hindrance and weakening (R"lR", R5OyohiR6H0-X bond) represents a substituted or unsubstituted alkyl group, and R3 and R4 represent the same or different straight-chain or branched substituted alkyl groups or R3CNCtR4 can be part of a cyclic structure which is another saturated A compound characterized in that it has a ring fused with a ring or an aromatic ring (the cyclic structure or the aromatic ring is optionally substituted). (2) The compound according to claim (1), in which the weakening of the ox bond occurs at moderate temperatures. (3) The group derived from x is: Yoshi (where R, R' and R'' are the same or different and are selected from hydrogen, alkyl, phenyl, cyano, carboxylic acid or carbocyclic group) The metal compound according to claim 1 or 2, which is in the form of (4), where X is tert-butyl, cyanisozorobyl, phenyl, methyl, or a substituted group thereof The compound according to any one of claims (1) or (2). (5) R' I R21R" and R6 are methyl, ethyl, propyl, ethyl, isozolobyl, isodityl,
The compound according to any one of claims (1) to (4), which is t-butyl, neopentyl, benzyl or a substituted group thereof. (61R3 and R4 are methyl, ethyl, propyl, butyl, isozolobyl, indityl, t-decha, pentyl, octadecyl, or if R30NCR4 is part of a cyclic structure, the cyclic structure is: (where n is from 1 to an integer of up to 10, preferably an integer of 1 to 6, including when such a cyclic group is substituted)
5) The compound described in any one of items up to item 5). (7) The nitroxy P group of formula (■) does not initiate any substantial free radical polymerization of the unsaturated monomer,
The compound according to any one of Items 1 to (6). (8) A compound according to any one of claims (1) to (7) bound to a polymer or incorporated into a monomer. (9) General structure of formula I: (wherein X represents a group having at least one carbon atom and the radical X , and the radical □ functionality is present on the carbon atom or one of the carbon atoms, Hl, R2, R5 and R6 are o-
x represents the same or different linear or branched substituted or unsubstituted alkyl group of sufficient chain length to provide steric hindrance and weakening of the bond, and R3 and R4 are the same or different linear or branched substitutions; R30NCR4 represents an alkyl group or can be part of a cyclic structure, which is fused to another saturated or aromatic ring (the cyclic structure or aromatic ring is optionally 1. A process for producing polymers or copolymers, especially oligomers, by free radical polymerization of unsaturated monomers, which comprises heating a compound having an unsaturated monomer (substituted). (0) to form a graft polymer comprising forming a polymer having an alkoxyamine group side chain of the general structure of Formula I and further adding a heptamer to form a graft copolymer by growth-controlled free radical polymerization. 2
Claim No. 9, characterized in that it consists of a stepwise method.
). 0D Two or more heptamers in which at least one monomer contains an alkoxyamine group having the general structure of formula
A method according to claim 9 for producing an alkoxyamine group-containing polymer comprising copolymerizing the following. 0ri The polymerization of the graft copolymer occurs as a free radical polymerization of stepwise growth without substantially producing a homopolymer of the added monomer, and as defined in any one of claims 9 to 9. Method described. 03) A polymer produced by the method according to any one of claims (9) to (12),
Especially oligomers. αa Is that the Blockco issue? The polymer according to claim 03), which is a remer. (15) The polymer according to claim α1], (13) or Oa, which is a graft copolymer. θ6) A device consisting of a free radical of the general structure of formula
) to α0 term. a′? ) A polymer according to any one of claims 0 to 10, further comprising an additional functional group capable of undergoing a reaction. The polymer according to any one of claims 1 to 19, which is an oligomer having a point-end group according to any one of claims 04) to 19.