CA2231398C - Control of molecular weight and end-group functionality in polymers - Google Patents
Control of molecular weight and end-group functionality in polymers Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Abstract
This invention relates to a process for the production of lower molecular weight polymers by free radical-initiated polymerization of unsaturated species characterised by the use of an unsaturated compound of Formula (I) as a chain transfer agent wherein R1 and R2 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or heterocyclic ring, and halogen; X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl; Y is selected from the group consisting of halogen, a polymer chain, and CR3R4Z, wherein R3 and R4 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring, and halogen; and Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl and optionally substituted arylsulfonyl; provided that when X is optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl, Y is not halogen. The invention also relates to various polymers produced by this process and products comprising these polymers. The process of the invention may also be used in the preparation of A-B type block copolymers.
Description
FUNCTIONALITY IN POLYMERS
The invention relates to processes for the production of polymers, including block, graft, homo and copolymers, of controlled molecular weight by free radical-initiated polymerization of unsaturated species in the presence of unsaturated halogen or sulfonyl-containing compounds, and such polymers with halogen or sulfonyl-containing end-groups produced by such processes. The polymers produced may also have olefinic end-groups.
The invention also relates to novel graft copolymers formed using the polymers from this process, and block copolymers produced by this process.
In polymerization processes, it is necessary to be able to control the molecular weight of the polymer so that the product may be fitted to a particular use or need. For example, when an uncontrolled polymerization tends to produce very high molecular weight polymers, it may be necessary to limit the molecular weight and this must be done in a predictable and controllable fashion. In addition, polymers of limited molecular weight are particularly useful as precursors in the manufacture of other polymeric materials and as additives or components of formulations for plastics, elastomers and surface coating compositions, as well as being useful in their own right in many applications.
In conventional free radical-initiated polymerization, there are a number of ways of molecular weight reduction leading to a solution to the above problems. The most common method involves the use of additional initiator which acts as a free radical source or the use of the normal quantity of initiator in conjunction with a chain transfer agent (hereinafter referred to as "CTA"). If a C'fA is used at least a part of this agent is incorporated into the polymer molecule. Ideally, molecular weight control must be achieved in such a way as to not introduce undesirable functionality into the polymer.
Although the use of CTAs offers a means of effecting molecular weight control, those in current use have a number of disadvantages. For example, the CTAs used in conventional free radical-initiated polymerization processes are alkanethiols which possess an objectionable odour and can lead to a wide distribution of molecular weights in batch polymerizations with certain monomers. Additionally, the use of thiols causes the incorporation of a sulphur atom into the polymer chain which can result in premature discoloration of the polymer, which is especially deleterious in the coatings industry.
Furthermore, there is little scope with thiols for the chain transfer constant to be optimized for some particular vinyl polymerizations. Carbon tetrachloride which is frequently used in the polymer industry as a CTA is falling into disuse because it is toxic and an ozone depleting substance.
Existing addition/fragmentation transfer agents such as substituted vinyl ethers and allyl sulphides assist in overcoming many of the disadvantages of thiols aid allow the installation I S of a number of different types of functional groups at the end of polymer molecules.
However, these agents may have inappropriate chain transfer constants and/or give significant retardation of polymerisation with methyl acryiate, vinyl acetate and vinyl halides.
Olefmic end-functional polymers (often called "macromonomers" or "macromers" ) are important as building-blocks for block and graft copolymers and polymer networks. Homo-and co-polymers of such macromers give rise to comb-type polymers with structures like those normally obtained by graft polymerization. Such homo- and co-polymers of macromers are useful inter alia as suspending/dispersing agents, compatibilisers or surfactants.
WO-A-95/12568 relates to a process for the free radical initiated polymerization of unsaturated species in the presence of a chain transfer agent of Formula (I).
Ry\C R X
CH2=C
Y
Formula 1 wherein Q, R3, R4, X, Y, and Z have the meanings as indicated in WO-A-95/12568.
Canadian Patent No. 1,094,746 describes "vinyl halide polymers of relatively low molecular weight are obtained when a monomer component comprising a vinyl halide is polymerization in the presence of a free radical generating polymerization initiator and a molecular weight regulating agent that is a polybromobutene.
Several chloroallyl transfer agents for use in vinyl acetate polymerization have been described e.g. allyl chloride, methallyl chloride, 3-chloro-3-methylbut-1-ene and 1-chloro-3-methylbut-2-ene. These compounds differ from those of the present invention in that they do not possess a substituent Y = halogen and they are described as giving significant.
The invention relates to processes for the production of polymers, including block, graft, homo and copolymers, of controlled molecular weight by free radical-initiated polymerization of unsaturated species in the presence of unsaturated halogen or sulfonyl-containing compounds, and such polymers with halogen or sulfonyl-containing end-groups produced by such processes. The polymers produced may also have olefinic end-groups.
The invention also relates to novel graft copolymers formed using the polymers from this process, and block copolymers produced by this process.
In polymerization processes, it is necessary to be able to control the molecular weight of the polymer so that the product may be fitted to a particular use or need. For example, when an uncontrolled polymerization tends to produce very high molecular weight polymers, it may be necessary to limit the molecular weight and this must be done in a predictable and controllable fashion. In addition, polymers of limited molecular weight are particularly useful as precursors in the manufacture of other polymeric materials and as additives or components of formulations for plastics, elastomers and surface coating compositions, as well as being useful in their own right in many applications.
In conventional free radical-initiated polymerization, there are a number of ways of molecular weight reduction leading to a solution to the above problems. The most common method involves the use of additional initiator which acts as a free radical source or the use of the normal quantity of initiator in conjunction with a chain transfer agent (hereinafter referred to as "CTA"). If a C'fA is used at least a part of this agent is incorporated into the polymer molecule. Ideally, molecular weight control must be achieved in such a way as to not introduce undesirable functionality into the polymer.
Although the use of CTAs offers a means of effecting molecular weight control, those in current use have a number of disadvantages. For example, the CTAs used in conventional free radical-initiated polymerization processes are alkanethiols which possess an objectionable odour and can lead to a wide distribution of molecular weights in batch polymerizations with certain monomers. Additionally, the use of thiols causes the incorporation of a sulphur atom into the polymer chain which can result in premature discoloration of the polymer, which is especially deleterious in the coatings industry.
Furthermore, there is little scope with thiols for the chain transfer constant to be optimized for some particular vinyl polymerizations. Carbon tetrachloride which is frequently used in the polymer industry as a CTA is falling into disuse because it is toxic and an ozone depleting substance.
Existing addition/fragmentation transfer agents such as substituted vinyl ethers and allyl sulphides assist in overcoming many of the disadvantages of thiols aid allow the installation I S of a number of different types of functional groups at the end of polymer molecules.
However, these agents may have inappropriate chain transfer constants and/or give significant retardation of polymerisation with methyl acryiate, vinyl acetate and vinyl halides.
Olefmic end-functional polymers (often called "macromonomers" or "macromers" ) are important as building-blocks for block and graft copolymers and polymer networks. Homo-and co-polymers of such macromers give rise to comb-type polymers with structures like those normally obtained by graft polymerization. Such homo- and co-polymers of macromers are useful inter alia as suspending/dispersing agents, compatibilisers or surfactants.
WO-A-95/12568 relates to a process for the free radical initiated polymerization of unsaturated species in the presence of a chain transfer agent of Formula (I).
Ry\C R X
CH2=C
Y
Formula 1 wherein Q, R3, R4, X, Y, and Z have the meanings as indicated in WO-A-95/12568.
Canadian Patent No. 1,094,746 describes "vinyl halide polymers of relatively low molecular weight are obtained when a monomer component comprising a vinyl halide is polymerization in the presence of a free radical generating polymerization initiator and a molecular weight regulating agent that is a polybromobutene.
Several chloroallyl transfer agents for use in vinyl acetate polymerization have been described e.g. allyl chloride, methallyl chloride, 3-chloro-3-methylbut-1-ene and 1-chloro-3-methylbut-2-ene. These compounds differ from those of the present invention in that they do not possess a substituent Y = halogen and they are described as giving significant.
retardation. The transfer agents described in the present invention also have transfer constants appropriate for use with vinyl acetate, vinyl chloride and methyl acrylate polymerization.
According to one aspect of the present invention there is provided a process for the production of lower molecular weight polymers by free radical-initiated polymerization of unsaturated species characterized by the use of an unsaturated compound of Formula I as a chain transfer agent:
IO R1~C R X
CH2=C
Y
Formula I
wherein Rl and RZ a.re the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring and halogen;
X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl, Y is selected from the group consisting of halogen, a polymer chain and CR3R4Z, wherein R3 and R4 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or heterocyclic ring, and halogen; and Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl and optionally substituted arylsulfonyl;
= provided that when X is optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl, Y is not halogen.
In a preferred embodiment Rl and R2 are selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, phenyl, biphenyl, naphthyl, chlorine and w0 97/13792 PCT/AU96/Ofl622 fluorine. More preferably Ri and Rz are selected from hydrogen, methyl, phenyl, chlorine and fluorine. Most preferably Rl and RZ are both hydrogen.
Suitable alkylsulfonyl and arylsulfonyl include p-toluenesulfonyl ("tosyl"), methanesulfonyl ("mesyl"), trifluoromethanesulfonyl and benzenesulfonyl.
In a further preferred embodiment when Y is CR3R4Z, R3 and R4 are selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, phenyl, biphenyl, naphthyl, tosyl, mesyl, trifluoromethanesulfonyl, benzenesulfonyl, chlorine and fluorine. More preferably R3 and R4 are selected from hydrogen, methyl, phenyl, tosyl, mesyl, chlorine and fluorine. Most preferably R3 and R4 are both hydrogen.
According to another aspect of the present invention there is provided the use of an unsaturated compound of general Formula I as a chain transfer agent in a process for the production of lower molecular weight polymers by free radical-initiated polymerization of an unsaturated species.
The term "optionally substituted" as used herein means that a group may or may not be substituted with one or more substituents which do not interfere with or parkicipate in the polymerization process. Examples of such substituents include alkyl, aryl, hydroxyalkyl, aminoalkyl, carboxylic acid, ester, acyloxy, amide, nitrite, haloalkyl, alkoxy, phosphonate, sulfonate, silyl or silyloxy group. When used in relation to a moiety containing a ring, the term "optionally substituted" further means that the moiety may or may not have substituent groups directly or indirectly attached to the ring by means of a methylene group or other side chain. Any such substituent groups do not take part in the actual lowering of the molecular weight but may be capable of subsequent chemical reaction. If the substituent is capable of subsequent reaction, the lower molecular weight polymer containing such reactive substituent group is thereby able to undergo further chemical transformation, such as being joined with another polymer chain. Suitable reactive substituents includes hydroxy, amino, halogen, allyl, cyano, epoxy, carboxylic acid and its derivatives, such as esters and the like.
The optionally substituted alkyl groups may contain up to 32 carbon atoms and be straight chained or branched. Examples of straight chained and branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, l, l-dimethylpropyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2,-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3,-trimethylbutyl, 1,1,2- -trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, S-, 6-, 7- and 8-methylnonyl, 1-, 2-, 3-, 4-, S- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-1 S methyldecyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, S- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1-2-pentylheptyl and the like.
The term "saturated or aromatic carbocyclic or heterocyclic ring" is used herein in its broadest sense to denote a mono- or poly-cyclic ring structure containing from 3 to 14 atoms, and includes cyclic alkyl, heterocyclyl, aryl and heteroaryl moieties.
Examples of "cyclic alkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Examples of "heterocyclyl"
include pyrrolidinyl, morpholinyl, thiomorpholinyl, or partially hydrogenated thienyl, furanyl, pyrrolyl, pyrazolyl, oxazolyl, oxazinyl, thiazinyl, pyridinyl, azepinyl and the like.
Examples of aryl include phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl and the like . Phenyl is a preferred aryl group. Examples of "heteroaryl" include pyridyl, furanyl, thienyl, pyrrolyl, benzthiazolyl, indolyl, w0 97/13792 PCT/AU96/00622 _6_ benzofuranyl, benzothiophenyl, pyrazinyl, quinolyl, pyrimidinyl and the like.
The phrase "polymers of lower molecular weight" and "lower molecular weight polymers"
as used herein means polymers whose molecular weight is lower than that of the corresponding polymer prepared in the absence of a CTA. The molecular weight of a polymer from a given reaction is dependent upon the ratio of chain transfer agent to monomer. The greater the ratio of CTA to monomer, the lower the molecular weight. The appropriate ratio can be readily calculated using the chain transfer constant for the CTA/monomer combination.
The term "polymer chain" as used herein is used in its broadest sense to mean a molecular chain composed of a series of monomers. Examples of monomers from which the polymer chain can be composed include vinyl esters, vinyl halides, vinyl aromatics, vinylidene halides, acrylic esters, methacrylic esters, unsaturated polyunsaturated hydrocarbons. The polymer chain may also be composed of mixtures of these monomers.
The process of the invention uses the compounds of Formula I as alternatives to thiols or other CTAs such as carbon tetrachloride, to produce polymers of a desired molecular weight with the added advantage that the amount of CTA needed to give a product polymer of a desired molecular weight may be reliably calculated from the chain transfer constant. The compounds of Formula I may be added in pure form or mixed with diluents that allow safer and easier handling. In certain circumstances the compounds of Formula I may also be used in conjunction with conventional chain transfer agents, such as thiols, carbon tetrachloride etc. The process of the invention may be readily adopted by the users of conventional processes using thiols. Little change in the reaction conditions is required other than the substitution of the appropriate quantity of the compound of Formula I for the thiol. The proportion of the compound of Formula I used may be in the range of about 0.01 to about mole percent based on total monomer, with a preferred range about 0.1 to about 10 mole percent.
_7_ The process may be operated under the reaction conditions appropriate for free radical-initiated polymerization, i.e., temperatures from about -100°C to about 200°C and pressures from below atmospheric to substantially above atmospheric.
The polymerization process can be carried out in bulk, solution, emulsion, suspension or other conventional polymerization modes (batch, semi-batch, continuous or feed process).
Sources of free radicals for polymerization processes would be apparent to the person skilled in the art and may include, thermal initiators, such as, a,a'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylpentanenitrile), benzoyl peroxide, t-butyl peroxybenzoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, ammonium persulfate and potassium persulfate; photoinitiators, such as, benzoin derivatives, acyl phosphine oxides and champhorquinone tertiary amine; and redox initiators, such as, hydrogen peroxide in combination with a transition metal. Other suitable initiator systems are described in G. Moad and D. Solomon "Chemistry of Free Radical Polymerization"
Elsevier, Oxford 1995.
Any unsaturated species susceptible to free radical-initiated polymerization may be used although it should be noted that the chain transfer constant will vary with the species used.
The unsaturated species is preferably an unsaturated monomer including vinyl esters, vinyl halides, vinyl aromatics, vinylidene halides, acrylic esters, methacrylic esters, unsaturated or polyunsaturated hydrocarbons or mixtures thereof. Examples of these monomers are vinyl esters such as vinyl acetate or vinyl butyrate; vinyl halides such as vinyl chloride or vinyl bromide; vinylidene halides such as vinylidene chloride, vinylidene bromide, alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or 2-ethylhexyl methacrylate; acrylonifrile; methacrylonitrile; vinyl aromatics such as styrene, p-chloromethylstyrene, 2-vinylpyridine, 4-vinylpyridine or N-vinylpyrrolidone;
vinyl ethers such as CH2 CHOR wherein R is optionally substituted alkyl; or allyl monomers such as allyl ethers, allyl carbonates or diallyl carbonates.
-$_ The process of the invention may be used to prepare polymers with chloro-, bromo-alkylsulfonyl or arylsulfonyl end groups which may be used as the basis for further modification of the polymer. For example, Bamford et al. ( Bamford, C H, Eastmond, G
C, Woo, J, Richards D H, Polymer Communications 1982, ~ 643) describes a process whereby polymers with bromo- or chloro-end groups may be converted to propagating radicals and thus used to synthesise block copolymers. Such block copolymers also form part of the present invention.
In a further aspect of the present invention there is provided a process for preparing an A-B
type block copolymer by free radical-initiated polymerization of a first unsaturated species in the presence of a first chain transfer agent of Formula I:
R~\C R X
I
CH2=C
Y
Formula 1 wherein R' and R2 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, and halogen;
X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl;
Y is CR3R'Z, wherein R' and R' may be the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, and halogen; .
R' to R' maybe optionally substituted saturated or aromatic carbocyclic or aromatic ring; and Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsuIfonyl, and optionally substituted arylsulfonyl; provided that R' and RZ are both hydrogen and/or R3 and R' are both hydrogen;
to produce a second chain transfer agent of Formula I wherein Y is a polymer chain, and _9_ polymerizing a second unsaturated species in the presence of the second chain transfer agent to produce an A-B type block copolymer of said first and second unsaturated species. In the first chain transfer agent it is preferred that Rl, R2, R3 and R4 are each hydrogen.
In this process the transfer agent of Formula I is being used as a "tandem chain transfer agent" agent. This type of process for the formation of an A-B block copolymer is illustrated below in scheme 1 in which monomer A is vinyl acetate.
Tandem Chain Transfer of Trinyl Acetate First stage c! OAc + --cl CI-CH Z-CH ~CH2-CH ~CH 2 OAc OAc CI
Second stage polymerization Cl-CHz-CH -~CHy-CH ~--CHZ
I n oAc OAc CI
CI-CH Z-CH -~-CH y-CH ~--CH Z
~ ~ I n OAc OAc di-block copolymers Scheme I
y CA 02231398 1998-03-09 P:\OPER~bffC~IvIOLPC7LY1.SPE.30/9197 R E C E 1 V E D 3 ~ S EP 199?
The problem of the polymeric chain transfer agent reacting twice in the first stage to produce an A-A block copolymer, and the problem of high molecular weight homopolymer B
being produced once the polymeric chain transfer agent is exhausted, can be minimized or overcome by terminating the polymerizations at low conversions.
A further aspect of the process of the invention is that, unlike processes involving thiols or other CTAs, the present process is capable of directly and conveniently producing polymer chains with a terminal polymerizable olefinic end group. For example, the process of the invention can be used to prepare macromonomers, which are useful materials for the preparation of graft copolymers by methods known to the art.
The macromonomers produced may be reactive under the conditions of their production and copolymerise with the remaining monomer. This will limit the concentration of macromonomer obtainable; optimisation of macromonomer yield may require stopping the polymerization at low conversions or changing conditions to limit the reactivity of the olefinic bond of the macromonomer. On the other hand the macromonomer copolymer will be a hyperbranched or a comb polymer, if such is the desired product the reaction may be advantageously carried to high conversion.
The compounds of Formula I may be obtained from a commercial source or via a simple chemical modification of a commercial starting material.
The compounds of Formula 1 display a high activity in controlling molecular weight in polymerization reactions. The compounds 2,3-dichloropropene (la), 3-chloro-z-chloromethyl-1-propene (Ib), 2,3-dibromopropene (Ic), 3-bromo-2-bromomethyl-1-propene (Id), 2-bromo-3-chloropropene (Ie), 3-bromo-2-chloropropene (If), 3-chloro-2-fluoropropene (Ig), 3-bromo-2-fluoropropene (Ih), 2-(chloromethyl)-3-tosylpropene(Ii) and 3-tosyl-2-(tosylmethyl)propene(Ij) whose formulae are shown below, are examples of preferred compounds of Formula I:
AMENDED SHEET
IPEAJAU
/CHz-Cl ~CHZ-CI
CHz-C CHz-C
\C1 \CHZ-Cl (Ia) (Ib) /CHz-Br /CHZ-Br /CHZ-C1 CHI \ CHZ-C CHT- \
Br \CH2 -Br Br (Ic) (Id) (Ie) /CHZ-Br /CHZ-C1 /CHZ-Br CHz-=C CHi=-C CHIC
SCI \F \F
(I~ (IS) (Ih) O
O
,~- S o C ~O CH2-S O CH3 (~ ) CH2 -S ~ CH3 (I~) Compounds such as (Ia) and (Ib) of the general Formula I used in the process of the invention display an unexpectedly high activity in controlling molecular weight in polymerization reactions and have chain transfer constants that may be superior to those of thiols, particularly with vinyl acetate, vinyl chloride and alkyl acrylates.
Their activity is S such that their chain transfer constants can approach the optimum values for batch polymerizations and this activity is not as highly dependent as that of thiols on the structure of the propagating radical. This enables synthesis of polymers with relatively low polydispersity (Mw/Mn <2).
The present process is applicable to the manufacture of synthetic polymers and other polymer formulations where reduced molecular weight and narrow polydispersity aids processing and improves properties. The process can also be used to produce low molecular weight polymers, oligomers, macromonomers and functional polymers for a variety of applications such as high-solid surface coatings, paints and adhesives.
Furthermore, the IS process can be used to enable better control over the polymerization kinetics, e.g., delaying the onset of gelation in cross-linking systems.
Thus, the present invention also provides lower molecular weight polymers, oligomers, macromonomers or functional polymers such as block or graft copolymers whenever produced by the process of the invention.
The present invention also extends to plastics, elastomers, surface coatings, paints, adhesives, compounding agents, modifiers or plasticizers compounding agents, modifiers or plasticizers which are composed wholly or partly of the lower molecular weight polymers whenever produced by the process of the invention.
The operation of this process is demonstrated by the following non-limiting examples. In these examples, molecular weight measurements were performed on a Waters Associates liquid chromatograph equipped with differential refractometer and six ,u-styragel columns of 106, 105, 104, 103, 500 and 100 ,~ pore size. Tetrahydrofuran solvent was used at a flow rate of 1 mL/min. Results were derived by comparison with polystyrene standards using the Chromatix GPC-1 program. The conversions were determined from the mass of the polymers isolated after removal of all the volatiles in vacuo and after subtracting the mass of the CTAs.
The following non-limiting examples illustrate the use of the invention to produce polymers of controlled molecular weight with olefmic, halogen or sulfonyl containing end groups.
Example 1: Preparation of controlled Molecular Weight Olefin-Terminated Polymers of Irinyl Acetate Using 2, 3 Dichloropropene (la) and 3-Chloro-2-chloromethyl-1 propene (Ib) Polymerizations of vinyl acetate (VAc) were carried out in vacuo at 60°C for one hour using the following procedure. a,a'-Azobis-isobutyronitrile (17.4 mg) was dissolved in freshly distilled vinyl acetate (100 mL). Aliquots (10 mL) were removed and added to ampoules containing weighed amounts of CTA [(Ia) or (Ib)). After the polymerization, the volatiles were removed and the polymers were dried and examined (see Table 1 below).
Proton nuclear magnetic resonance spectroscopy was performed on a low molecular weight sample of polyvinyl acetate) (entry 9 Table 1; M" 2940) using CTA (Ia). The IH-NMR
spectrum showed signals at 8 3.60-3.85 ppm (multiplets) and 5.20-5.25 ppm which were consistent with the presence of a chloromethylene and an olefinic C=CH2 end group respectively. Similarly, a low molecular weight sample of polyvinyl acetate) (M,14325) prepared by the CTA (Ib) showed signals at S 3.40-3.60 ppm (multiplets), 4.00 ppm (multiplets) and 4.90, 5.15 ppm (singlet each) which were consistent with the presence of two chloromethylene end groups and an olefinic group.
dV0 97/13792 PCT/AU96/00622 Table l:
lhlolecular Weights and Conversions for hinyl Acetate Polymerizations Carried Out at 60°C
in the Presence of CTAs (Ia) and (Ib) Example Time 103[CTA]/
No. CTA (hr.) [Monomer] Conv. M# M /M"
w 1.1 Ia 1.0 0.00 15.0 117 120 1.8 1.2 Ia 1.0 0.40 14.7 108 800 1.9 1.3 Ia 1.0 0.82 12.3 78 000 1.8 1.4 Ia 1.0 1.23 9.4 36 920 1.9 1:5 Ia 1.0 1.28 7.3 37 060 1.9 1 1.6 Ia I .0 2.53 2.0 9 980 2.2 S
1.7 Ia 1.0 3.83 1.3 7 400 1.9 1.8 Ia 1.0 4.19 2.17 7 960 1.8 1.9 Ia 2.0 13.4 1.3 2 940 1.6 1.10 Ib 1.0 0.00 14.7 13 8 220 2.0 1.11 Ib 1.0 1.16 9.7 22 870 1.8 1.12 Ib 1.0 2.21 7.6 11 430 1.8 1.13 Ib 1.0 3.37 6.4 7180 1.8 1.14 Ib 2.0 6.06 6.6 4 325 1.65 Y
# Polystyrene standard equivalent number-average molecular weight.
Example 2: Polymerization of Controlled Molecular Weight Polymers ofMethyl Acrylate Using CTAs (Ia) and (1b) Polymerizations of methyl acrylate (MA) were carned out using a stock solution prepared from a,a'-azobisisobutyronitrile (6.5 mg) and distilled methyl acrylate (10 mL).
Aliquots (2 mL) were removed and added to ampoules containing thiophene-free benzene (8 mL), and weighed amounts of the CTAs (Ia) or (Ib). After degassing, the mixtures were polymerized at 60°C for one hour. The volatiles were then removed on rotary evaporator and the polymers were dried in vacuo to constant weight and examined by GPC (see Table 2 below).
Table 2:
Molecular Weights and Corrve~ siorzs for Methyl Acrylate Polymerizatiorrs Carried Out at 60 ° C
for 1 hour in the Presence of CTAs (la) and (Ib) Example 102[CTA]/
No. CTA [Monomer] Convers'n Mn# MwMir, 21. la 0.00 32.2 684 470 1.9 2.1 la 1.22 27.5 365 250 2.2 2.3 la 2.45 17.9 121 250 1.8 2.4 la 4.93 17.7 59 380 1.7 2.5 1b 0.00 32.3 684 470 1.9 2.6 Ib 1.09 18.6 135 280 1.7 2.7 1b 2.22 22.8 66 820 1.8 2.8 1b 4.39 20.2 38 350 1.7 # Polystyrene standard equivalent number-average molecular weight.
WO 97/13792 PCT/AiT96/00622 As shown in Table 2 above, the molecular weight of the resulting polymer may be reduced to below 10% of the molecular weight in the absence of CTA.
Table 3 summarizes the results of chain transfer constants in polymerizations of vinyl acetate (VAc) and methyl acrylate (MA) using the CTAs (Ia) and (Ib).
Table 3:
Chain Transfer Constants (C~ for Polymerizations of Common Monomers in the Presence of CTAs Monomer CTA Temperature Chain Transfer Constants (Cx) 'VAc Ia 60 ° C 1.23 Ib 60°C 3.39 Ia 60 ° C 0.03 60°C 0.05 Example 3 : Graft Copolymer Polyvinyl acetate) graft- poly(methyl acrylate) Polyvinyl acetate) macromonomer [produced by the present invention using CTA
(Ia)] (1V1"
According to one aspect of the present invention there is provided a process for the production of lower molecular weight polymers by free radical-initiated polymerization of unsaturated species characterized by the use of an unsaturated compound of Formula I as a chain transfer agent:
IO R1~C R X
CH2=C
Y
Formula I
wherein Rl and RZ a.re the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring and halogen;
X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl, Y is selected from the group consisting of halogen, a polymer chain and CR3R4Z, wherein R3 and R4 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or heterocyclic ring, and halogen; and Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl and optionally substituted arylsulfonyl;
= provided that when X is optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl, Y is not halogen.
In a preferred embodiment Rl and R2 are selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, phenyl, biphenyl, naphthyl, chlorine and w0 97/13792 PCT/AU96/Ofl622 fluorine. More preferably Ri and Rz are selected from hydrogen, methyl, phenyl, chlorine and fluorine. Most preferably Rl and RZ are both hydrogen.
Suitable alkylsulfonyl and arylsulfonyl include p-toluenesulfonyl ("tosyl"), methanesulfonyl ("mesyl"), trifluoromethanesulfonyl and benzenesulfonyl.
In a further preferred embodiment when Y is CR3R4Z, R3 and R4 are selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, phenyl, biphenyl, naphthyl, tosyl, mesyl, trifluoromethanesulfonyl, benzenesulfonyl, chlorine and fluorine. More preferably R3 and R4 are selected from hydrogen, methyl, phenyl, tosyl, mesyl, chlorine and fluorine. Most preferably R3 and R4 are both hydrogen.
According to another aspect of the present invention there is provided the use of an unsaturated compound of general Formula I as a chain transfer agent in a process for the production of lower molecular weight polymers by free radical-initiated polymerization of an unsaturated species.
The term "optionally substituted" as used herein means that a group may or may not be substituted with one or more substituents which do not interfere with or parkicipate in the polymerization process. Examples of such substituents include alkyl, aryl, hydroxyalkyl, aminoalkyl, carboxylic acid, ester, acyloxy, amide, nitrite, haloalkyl, alkoxy, phosphonate, sulfonate, silyl or silyloxy group. When used in relation to a moiety containing a ring, the term "optionally substituted" further means that the moiety may or may not have substituent groups directly or indirectly attached to the ring by means of a methylene group or other side chain. Any such substituent groups do not take part in the actual lowering of the molecular weight but may be capable of subsequent chemical reaction. If the substituent is capable of subsequent reaction, the lower molecular weight polymer containing such reactive substituent group is thereby able to undergo further chemical transformation, such as being joined with another polymer chain. Suitable reactive substituents includes hydroxy, amino, halogen, allyl, cyano, epoxy, carboxylic acid and its derivatives, such as esters and the like.
The optionally substituted alkyl groups may contain up to 32 carbon atoms and be straight chained or branched. Examples of straight chained and branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, l, l-dimethylpropyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2,-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3,-trimethylbutyl, 1,1,2- -trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, S-, 6-, 7- and 8-methylnonyl, 1-, 2-, 3-, 4-, S- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-1 S methyldecyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, S- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1-2-pentylheptyl and the like.
The term "saturated or aromatic carbocyclic or heterocyclic ring" is used herein in its broadest sense to denote a mono- or poly-cyclic ring structure containing from 3 to 14 atoms, and includes cyclic alkyl, heterocyclyl, aryl and heteroaryl moieties.
Examples of "cyclic alkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Examples of "heterocyclyl"
include pyrrolidinyl, morpholinyl, thiomorpholinyl, or partially hydrogenated thienyl, furanyl, pyrrolyl, pyrazolyl, oxazolyl, oxazinyl, thiazinyl, pyridinyl, azepinyl and the like.
Examples of aryl include phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl and the like . Phenyl is a preferred aryl group. Examples of "heteroaryl" include pyridyl, furanyl, thienyl, pyrrolyl, benzthiazolyl, indolyl, w0 97/13792 PCT/AU96/00622 _6_ benzofuranyl, benzothiophenyl, pyrazinyl, quinolyl, pyrimidinyl and the like.
The phrase "polymers of lower molecular weight" and "lower molecular weight polymers"
as used herein means polymers whose molecular weight is lower than that of the corresponding polymer prepared in the absence of a CTA. The molecular weight of a polymer from a given reaction is dependent upon the ratio of chain transfer agent to monomer. The greater the ratio of CTA to monomer, the lower the molecular weight. The appropriate ratio can be readily calculated using the chain transfer constant for the CTA/monomer combination.
The term "polymer chain" as used herein is used in its broadest sense to mean a molecular chain composed of a series of monomers. Examples of monomers from which the polymer chain can be composed include vinyl esters, vinyl halides, vinyl aromatics, vinylidene halides, acrylic esters, methacrylic esters, unsaturated polyunsaturated hydrocarbons. The polymer chain may also be composed of mixtures of these monomers.
The process of the invention uses the compounds of Formula I as alternatives to thiols or other CTAs such as carbon tetrachloride, to produce polymers of a desired molecular weight with the added advantage that the amount of CTA needed to give a product polymer of a desired molecular weight may be reliably calculated from the chain transfer constant. The compounds of Formula I may be added in pure form or mixed with diluents that allow safer and easier handling. In certain circumstances the compounds of Formula I may also be used in conjunction with conventional chain transfer agents, such as thiols, carbon tetrachloride etc. The process of the invention may be readily adopted by the users of conventional processes using thiols. Little change in the reaction conditions is required other than the substitution of the appropriate quantity of the compound of Formula I for the thiol. The proportion of the compound of Formula I used may be in the range of about 0.01 to about mole percent based on total monomer, with a preferred range about 0.1 to about 10 mole percent.
_7_ The process may be operated under the reaction conditions appropriate for free radical-initiated polymerization, i.e., temperatures from about -100°C to about 200°C and pressures from below atmospheric to substantially above atmospheric.
The polymerization process can be carried out in bulk, solution, emulsion, suspension or other conventional polymerization modes (batch, semi-batch, continuous or feed process).
Sources of free radicals for polymerization processes would be apparent to the person skilled in the art and may include, thermal initiators, such as, a,a'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylpentanenitrile), benzoyl peroxide, t-butyl peroxybenzoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, ammonium persulfate and potassium persulfate; photoinitiators, such as, benzoin derivatives, acyl phosphine oxides and champhorquinone tertiary amine; and redox initiators, such as, hydrogen peroxide in combination with a transition metal. Other suitable initiator systems are described in G. Moad and D. Solomon "Chemistry of Free Radical Polymerization"
Elsevier, Oxford 1995.
Any unsaturated species susceptible to free radical-initiated polymerization may be used although it should be noted that the chain transfer constant will vary with the species used.
The unsaturated species is preferably an unsaturated monomer including vinyl esters, vinyl halides, vinyl aromatics, vinylidene halides, acrylic esters, methacrylic esters, unsaturated or polyunsaturated hydrocarbons or mixtures thereof. Examples of these monomers are vinyl esters such as vinyl acetate or vinyl butyrate; vinyl halides such as vinyl chloride or vinyl bromide; vinylidene halides such as vinylidene chloride, vinylidene bromide, alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or 2-ethylhexyl methacrylate; acrylonifrile; methacrylonitrile; vinyl aromatics such as styrene, p-chloromethylstyrene, 2-vinylpyridine, 4-vinylpyridine or N-vinylpyrrolidone;
vinyl ethers such as CH2 CHOR wherein R is optionally substituted alkyl; or allyl monomers such as allyl ethers, allyl carbonates or diallyl carbonates.
-$_ The process of the invention may be used to prepare polymers with chloro-, bromo-alkylsulfonyl or arylsulfonyl end groups which may be used as the basis for further modification of the polymer. For example, Bamford et al. ( Bamford, C H, Eastmond, G
C, Woo, J, Richards D H, Polymer Communications 1982, ~ 643) describes a process whereby polymers with bromo- or chloro-end groups may be converted to propagating radicals and thus used to synthesise block copolymers. Such block copolymers also form part of the present invention.
In a further aspect of the present invention there is provided a process for preparing an A-B
type block copolymer by free radical-initiated polymerization of a first unsaturated species in the presence of a first chain transfer agent of Formula I:
R~\C R X
I
CH2=C
Y
Formula 1 wherein R' and R2 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, and halogen;
X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl;
Y is CR3R'Z, wherein R' and R' may be the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, and halogen; .
R' to R' maybe optionally substituted saturated or aromatic carbocyclic or aromatic ring; and Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsuIfonyl, and optionally substituted arylsulfonyl; provided that R' and RZ are both hydrogen and/or R3 and R' are both hydrogen;
to produce a second chain transfer agent of Formula I wherein Y is a polymer chain, and _9_ polymerizing a second unsaturated species in the presence of the second chain transfer agent to produce an A-B type block copolymer of said first and second unsaturated species. In the first chain transfer agent it is preferred that Rl, R2, R3 and R4 are each hydrogen.
In this process the transfer agent of Formula I is being used as a "tandem chain transfer agent" agent. This type of process for the formation of an A-B block copolymer is illustrated below in scheme 1 in which monomer A is vinyl acetate.
Tandem Chain Transfer of Trinyl Acetate First stage c! OAc + --cl CI-CH Z-CH ~CH2-CH ~CH 2 OAc OAc CI
Second stage polymerization Cl-CHz-CH -~CHy-CH ~--CHZ
I n oAc OAc CI
CI-CH Z-CH -~-CH y-CH ~--CH Z
~ ~ I n OAc OAc di-block copolymers Scheme I
y CA 02231398 1998-03-09 P:\OPER~bffC~IvIOLPC7LY1.SPE.30/9197 R E C E 1 V E D 3 ~ S EP 199?
The problem of the polymeric chain transfer agent reacting twice in the first stage to produce an A-A block copolymer, and the problem of high molecular weight homopolymer B
being produced once the polymeric chain transfer agent is exhausted, can be minimized or overcome by terminating the polymerizations at low conversions.
A further aspect of the process of the invention is that, unlike processes involving thiols or other CTAs, the present process is capable of directly and conveniently producing polymer chains with a terminal polymerizable olefinic end group. For example, the process of the invention can be used to prepare macromonomers, which are useful materials for the preparation of graft copolymers by methods known to the art.
The macromonomers produced may be reactive under the conditions of their production and copolymerise with the remaining monomer. This will limit the concentration of macromonomer obtainable; optimisation of macromonomer yield may require stopping the polymerization at low conversions or changing conditions to limit the reactivity of the olefinic bond of the macromonomer. On the other hand the macromonomer copolymer will be a hyperbranched or a comb polymer, if such is the desired product the reaction may be advantageously carried to high conversion.
The compounds of Formula I may be obtained from a commercial source or via a simple chemical modification of a commercial starting material.
The compounds of Formula 1 display a high activity in controlling molecular weight in polymerization reactions. The compounds 2,3-dichloropropene (la), 3-chloro-z-chloromethyl-1-propene (Ib), 2,3-dibromopropene (Ic), 3-bromo-2-bromomethyl-1-propene (Id), 2-bromo-3-chloropropene (Ie), 3-bromo-2-chloropropene (If), 3-chloro-2-fluoropropene (Ig), 3-bromo-2-fluoropropene (Ih), 2-(chloromethyl)-3-tosylpropene(Ii) and 3-tosyl-2-(tosylmethyl)propene(Ij) whose formulae are shown below, are examples of preferred compounds of Formula I:
AMENDED SHEET
IPEAJAU
/CHz-Cl ~CHZ-CI
CHz-C CHz-C
\C1 \CHZ-Cl (Ia) (Ib) /CHz-Br /CHZ-Br /CHZ-C1 CHI \ CHZ-C CHT- \
Br \CH2 -Br Br (Ic) (Id) (Ie) /CHZ-Br /CHZ-C1 /CHZ-Br CHz-=C CHi=-C CHIC
SCI \F \F
(I~ (IS) (Ih) O
O
,~- S o C ~O CH2-S O CH3 (~ ) CH2 -S ~ CH3 (I~) Compounds such as (Ia) and (Ib) of the general Formula I used in the process of the invention display an unexpectedly high activity in controlling molecular weight in polymerization reactions and have chain transfer constants that may be superior to those of thiols, particularly with vinyl acetate, vinyl chloride and alkyl acrylates.
Their activity is S such that their chain transfer constants can approach the optimum values for batch polymerizations and this activity is not as highly dependent as that of thiols on the structure of the propagating radical. This enables synthesis of polymers with relatively low polydispersity (Mw/Mn <2).
The present process is applicable to the manufacture of synthetic polymers and other polymer formulations where reduced molecular weight and narrow polydispersity aids processing and improves properties. The process can also be used to produce low molecular weight polymers, oligomers, macromonomers and functional polymers for a variety of applications such as high-solid surface coatings, paints and adhesives.
Furthermore, the IS process can be used to enable better control over the polymerization kinetics, e.g., delaying the onset of gelation in cross-linking systems.
Thus, the present invention also provides lower molecular weight polymers, oligomers, macromonomers or functional polymers such as block or graft copolymers whenever produced by the process of the invention.
The present invention also extends to plastics, elastomers, surface coatings, paints, adhesives, compounding agents, modifiers or plasticizers compounding agents, modifiers or plasticizers which are composed wholly or partly of the lower molecular weight polymers whenever produced by the process of the invention.
The operation of this process is demonstrated by the following non-limiting examples. In these examples, molecular weight measurements were performed on a Waters Associates liquid chromatograph equipped with differential refractometer and six ,u-styragel columns of 106, 105, 104, 103, 500 and 100 ,~ pore size. Tetrahydrofuran solvent was used at a flow rate of 1 mL/min. Results were derived by comparison with polystyrene standards using the Chromatix GPC-1 program. The conversions were determined from the mass of the polymers isolated after removal of all the volatiles in vacuo and after subtracting the mass of the CTAs.
The following non-limiting examples illustrate the use of the invention to produce polymers of controlled molecular weight with olefmic, halogen or sulfonyl containing end groups.
Example 1: Preparation of controlled Molecular Weight Olefin-Terminated Polymers of Irinyl Acetate Using 2, 3 Dichloropropene (la) and 3-Chloro-2-chloromethyl-1 propene (Ib) Polymerizations of vinyl acetate (VAc) were carried out in vacuo at 60°C for one hour using the following procedure. a,a'-Azobis-isobutyronitrile (17.4 mg) was dissolved in freshly distilled vinyl acetate (100 mL). Aliquots (10 mL) were removed and added to ampoules containing weighed amounts of CTA [(Ia) or (Ib)). After the polymerization, the volatiles were removed and the polymers were dried and examined (see Table 1 below).
Proton nuclear magnetic resonance spectroscopy was performed on a low molecular weight sample of polyvinyl acetate) (entry 9 Table 1; M" 2940) using CTA (Ia). The IH-NMR
spectrum showed signals at 8 3.60-3.85 ppm (multiplets) and 5.20-5.25 ppm which were consistent with the presence of a chloromethylene and an olefinic C=CH2 end group respectively. Similarly, a low molecular weight sample of polyvinyl acetate) (M,14325) prepared by the CTA (Ib) showed signals at S 3.40-3.60 ppm (multiplets), 4.00 ppm (multiplets) and 4.90, 5.15 ppm (singlet each) which were consistent with the presence of two chloromethylene end groups and an olefinic group.
dV0 97/13792 PCT/AU96/00622 Table l:
lhlolecular Weights and Conversions for hinyl Acetate Polymerizations Carried Out at 60°C
in the Presence of CTAs (Ia) and (Ib) Example Time 103[CTA]/
No. CTA (hr.) [Monomer] Conv. M# M /M"
w 1.1 Ia 1.0 0.00 15.0 117 120 1.8 1.2 Ia 1.0 0.40 14.7 108 800 1.9 1.3 Ia 1.0 0.82 12.3 78 000 1.8 1.4 Ia 1.0 1.23 9.4 36 920 1.9 1:5 Ia 1.0 1.28 7.3 37 060 1.9 1 1.6 Ia I .0 2.53 2.0 9 980 2.2 S
1.7 Ia 1.0 3.83 1.3 7 400 1.9 1.8 Ia 1.0 4.19 2.17 7 960 1.8 1.9 Ia 2.0 13.4 1.3 2 940 1.6 1.10 Ib 1.0 0.00 14.7 13 8 220 2.0 1.11 Ib 1.0 1.16 9.7 22 870 1.8 1.12 Ib 1.0 2.21 7.6 11 430 1.8 1.13 Ib 1.0 3.37 6.4 7180 1.8 1.14 Ib 2.0 6.06 6.6 4 325 1.65 Y
# Polystyrene standard equivalent number-average molecular weight.
Example 2: Polymerization of Controlled Molecular Weight Polymers ofMethyl Acrylate Using CTAs (Ia) and (1b) Polymerizations of methyl acrylate (MA) were carned out using a stock solution prepared from a,a'-azobisisobutyronitrile (6.5 mg) and distilled methyl acrylate (10 mL).
Aliquots (2 mL) were removed and added to ampoules containing thiophene-free benzene (8 mL), and weighed amounts of the CTAs (Ia) or (Ib). After degassing, the mixtures were polymerized at 60°C for one hour. The volatiles were then removed on rotary evaporator and the polymers were dried in vacuo to constant weight and examined by GPC (see Table 2 below).
Table 2:
Molecular Weights and Corrve~ siorzs for Methyl Acrylate Polymerizatiorrs Carried Out at 60 ° C
for 1 hour in the Presence of CTAs (la) and (Ib) Example 102[CTA]/
No. CTA [Monomer] Convers'n Mn# MwMir, 21. la 0.00 32.2 684 470 1.9 2.1 la 1.22 27.5 365 250 2.2 2.3 la 2.45 17.9 121 250 1.8 2.4 la 4.93 17.7 59 380 1.7 2.5 1b 0.00 32.3 684 470 1.9 2.6 Ib 1.09 18.6 135 280 1.7 2.7 1b 2.22 22.8 66 820 1.8 2.8 1b 4.39 20.2 38 350 1.7 # Polystyrene standard equivalent number-average molecular weight.
WO 97/13792 PCT/AiT96/00622 As shown in Table 2 above, the molecular weight of the resulting polymer may be reduced to below 10% of the molecular weight in the absence of CTA.
Table 3 summarizes the results of chain transfer constants in polymerizations of vinyl acetate (VAc) and methyl acrylate (MA) using the CTAs (Ia) and (Ib).
Table 3:
Chain Transfer Constants (C~ for Polymerizations of Common Monomers in the Presence of CTAs Monomer CTA Temperature Chain Transfer Constants (Cx) 'VAc Ia 60 ° C 1.23 Ib 60°C 3.39 Ia 60 ° C 0.03 60°C 0.05 Example 3 : Graft Copolymer Polyvinyl acetate) graft- poly(methyl acrylate) Polyvinyl acetate) macromonomer [produced by the present invention using CTA
(Ia)] (1V1"
7,960; 0.4 g) was copolymerized with methyl acrylate (1.0 mL) in sulfur free benzene (5.0 mL) using AIBN (15.3 mg) as a free radical initiator. The copolymerization was carried out at 60°C for three hours to yield the title graft copolymer (M" 79,100;
1.2 g).
Example 4: Polymerization of hinyl Acetate by Feed Process A three-necked reactor was equipped with a reflux condenser and a pressure equalizing funnel with metering valve. The reactor was held under nitrogen positive pressure and the following ingredients were used.
Vinyl Acetate 50 ml Methanol 10 ml arf 2 CTA (Ia) 100 mg (Ex 4.1) or 505 mg (Ex 4. 2) AIBN 8.7 mg Methanol Sml Part 1 was charged to the reactor and heated to reflux (oil bath temperature was set at 80°C) under nitrogen atmosphere. When the temperature stabilized for 10 minutes, part 2 was charged to the reactor over 100 minutes via a pressure equalizing funnel with metering valve. Then the reaction mixture was held for further 3 hours (Example 4.1) or 24 hours (Example 4.2). The solvent and unreacted monomer were then distilled off. The results are summarized in Table 4 below. In the absence of CTA, the polymerization of vinyl acetate initiated by AIBN (total reaction time: two hours and forty minutes) in methanol gave polyvinyl acetate) with M" 131 380 and 34% conversion. The results in Table 4 below demonstrate that the molecular weight can be halved without decreasing conversion of monomer to polymer.
Table 4 ' Example CTA(Ia) Mn Ma, % Conv.
No.
4.1 100 mg 95 190 250 555 34.4 4.2 SOS mg 62 580 215 130 43.1 w0 97/13792 PCT/AU96/00622 Example 5: Preparation of Controlled Molecular Weight Poly(Yinyl Chloride) Using 2, 3 Dichloropropene (1a) Suspension polymerization of vinyl chloride was carried out using the following procedure.
S First, 25 L of water, 8.5 g of bis(4-t-butylcyclohexyl) peroxydica.rbonate, 40 mL of a suspending agent (4% Alcorex 72.5) and an appropriate amount of 2,3-dichloro-1-propene chain transfer agent (CTA, see Table 5) were charged in sequence into a 40 L
stainless-steel reactor and then the agitator was started at 300 rev/min. At this stage, the reactor was maintained under reduced pressure for a few minutes and then 3.15 Kg vinyl chloride monomer was charged to the reactor. The agitator speed was increased to 575 rev/min and the temperature of the mixture raised to SO°C. The polymerization was conducted at 50°C and a pressure of 690 kPa for 3.5 hours. The resulting product was separated by centrifuging, washed, dried and analyzed.
The conversion and molecular weight data are tabulated in the Table S.
Table S
Molecular weights and conversions for vinyl chloride polymerizations carried out in the presence of 2, 3 Dichloropropene (la) example 1C1'A~
LQ % Conv. M" Mw K value*
5.1 0 40.6 71,630 134,230 70.3 _ 5.2 0.2 30 65,870 137,880 68.5 5.3 1.0 30 41,420 90,530 50.2 * a measure of molecular weight from the equation:
75 KZxlO's leg 1~ _ - + K x 10-3 C
1 +l.SKcx 10-~
WO 97!13792 PCT/AU96/00622 Example 6: Preparation of Controlled Molecular Weight Olefin-Terminated Polymers of Vinyl Acetate Using 3-bromo-2-chloroprop-1-ene (I,fi ,~ nthesis of 3-bromo-2-chloroprop-1-ene (If!
A mixture of 2,3-dichloropropene (5.5g, 49.5 mmol), sodium bromide 5.16g) and ethyl bromide (37mL, 495 mmol) in DMF (60mL) was allowed to heat at 80°C for 27 hours.
After cooling to room temperature, the reaction mixture was diluted with saturated sodium chloride solution, and extracted three times with petroleum spirit 30-40°C. The combined organic layer was washed with water twice and then once with brine. After drying (anhydrous MgS04) and removing solvent on a rotary evaporator, the title compound (If) was obtained (2.47g, 32%) after vacuum distillation in a Kugelrohr apparatus (set at 70°C, 25mmHg). 1H-NMR (CDCl3) 8 (ppm): 4.09 (s, 2H, CHaBr); 5.40 and 5.59 (2s, 2H, vinylic-H).
Polvmerizations The polymerisations were carried out for one hour in sealed glass tubes in vacuo at 60°C
with AIBN in the manner of example 1. The molecular weights and the chain transfer constants (C$) derived from the Mayo plots are summarized in Table 6.
Table 6:
Molecular weight data and chain transfer constant for polymerization of vinyl acetate in the presence of (I,~
S CTA Wt of C Wt of M n Mw~
CTA polymer ~mg) CH -Br 0 28.7 1.7566 177,048 2.4 /
CHz-C 11.1 0.1620 3,251 1.9 \C1 ' 20.4 0.0857 1,631 1.6 40.2 0.0406 1,240 1.4 f E D.,1..~+..~e..,..
... __i__ , - , --,, - ---- --1»~ . ...,......, uuuiva..a iuvicl.u10.1 W Gt~tl6.
Example 7:
Preparation of Controlled Molecular Weight Styrene Butadiene Rubber (SBR) by Emulsion Polymerization using 2, 3-Dichloropropene (Ia) Emulsion polymerization of Styrene-Butadiene was carried out using the standard conditions for polymerization of Styrene-Butadiene which requires oxygen free reaction I S conditions in bottle reactors rotated in a polymerization bath at approximately 4S RPM and S' C.
The procedure was as follows:
The following were added to 2S0 ml bottle reactors fitted with butyl rubber serum-cap liners:
Reactor Charge Deionized Water 9gg Styrene 14. Sg Butadiene 3 S.Sg DRS 40 (surfactant) 0.6758 Westvaco 1480 (surfactant) 1.5758 KOH 0.308 Darvan WAQ ( surfactant) O.OSOg KCl O.15g EDTA bis-sodium salt O.OOSg Sodium Dithionite 0.01258 2,3 Dichloropropene (CTA) (1q) O.OSSg Initiator Solution Deionized Water 2g NAFE 0.01 g ' Sodium Formaldehyde Sulfoxylate O.OSg Cumene Hydroperoxide 0.0758 After the bottle reactors with reactants as shown above are brought to equilibrium in the 5°C bath, the Initiator solution is added via syringe. A sample is withdrawn from the reactor at about 40% monomer conversion and analyzed for molecular weight by Gel Permeation Chromatography (GPC). The sample is stopped from further polymerization by the addition of diethylhydroxyl-amine (DEHA).
After sampling, the polymerization of the remaining emulsion is continued until it is stopped by addition of DEHA when the monomer conversion was about 60%.
A control polymerization was run in the same fashion but without CTA added.
All polymers produced were analyzed by GPC for molecular weight.
The conversion and molecular weight data are tabulated in the Table 7.
w0 97/13792 PCT/AU96/00622 Table 7: ' Molecular weights arid conversions for SBR polymerizatiorzs carried out in the presence of 2, 3-Dichloropropene (Ia) S
Example [CTA] Conversion M #
n No. % (% ) 7.1 0.0 40 358,900 1,187,100 7.2 0.0 62 ** **
7.3 0.11 40 263,000 1,012,000 7.4 0.11 62 234,200 992,795 # Polystyrene equivalent number molecular weight.
** Too high molecular weight to filter and run on GPC
Example 8: Preparation of controlled molecular weight poly(methyl methacrylate) using 2-(chloromethyl)-3-tosylpropene (a) Synthesis of 2-(chloromethyl)-3-tosylpropene A solution of 2-(chloromethyl)-3-chloropropene (3.13g, 25mmo1) and sodium ~-toluenesulfmate (4.60g, 25mmol) in methanol (SOmL) was heated under reflux for 24 hours.
The solvent was evaporated on a rotary evaporator and the residue was extracted between dichloromethane and water. The organic layer was dried (anhydrous MgS04) and evaporated to give crude product (4.7g) which, after purification by column chromatography on a silica-gel column using ethyl acetate/n-hexane 1:9 as eluent, gave pure product (2.7g, 44% yield). 1H-NMR (CDCl3) b (ppm): 2.46 (s, 3H, CH3Ar); 3.92 (s, 2H, CHaSO~; 4.19 (s, 2H, CHZCI); 5.02 (s, 1H, vinylic-H); 5.45 (s, 1H, vinylic-H);
7.37 and 7.77 (2d, 4H, ArH).
r (~,l Polymerizations Polymerizations of methyl methacrylate were carried out in air-free sealed glass tubes at 60°C with AIBN as initiator. The molecular weights and the chain transfer constant (C,) derived from a Mayo plot are given in Table 8.
Table 8:
Molecular weights and conversions for methyl methacrylate polymeriZations carried out in the presence of 2-(chloromethyl)-3-tosylpropene CTA Wt Cs Wt of Mn M
of CTA polymer (mg) (g) (5.5) 0 0.05 0.18 198,402 1.9 II
10.1 0.18 172,385 1.7 ( ~Z= ~ 20.0 0.16 126,022 1.9 p 40.1 0.18 107.121 1.75 This particular transfer agent exhibits weak activity with MMA.
Example 9: Preparation of controlled molecular weight polyvinyl acetate) using (tosyl)-3-tosylmethylpropene (a) Synthesis of 2-fosyl-3(tosl~lmethyl)propene In a 100mL round bottomed flask, 2-(chloromethyl)-3-chloropropene (1.25g, lOmmol), sodium ~-toluenesulfinate (5.34g, 30mmo1) were mixed in methanol (SOmL) and the WO 97/13792 PC'~/AU96/00622 resulting mixture was heated under reflux. The reaction was followed by thin layer chromatography (silica-gel plate) with ethyl acetate/n-hexane 1:3 as solvent.
After 3.5 days, water (50 mL) was added and the mixture of products precipitated out as creamy solids (2.8g). The pure title compound was obtained (2.198, 60%) after column chromatography on a silica-gel column using ethyl acetateJn-hexane 2:3 as eluent. iH-NMR
(CDCl3) 8(ppm): 2.45 (s, 6H, 2xCH3Ar); 3.99 (s, 4H, 2xCH2S0~; 5.17 (s, 2H, vinylic-H);
7.34 and 7.72 (2d, 8H, ArH).
(b) Polymerizations Polymerizations of vinyl acetate were carried out in air-free sealed glass tubes at 60 ° C with AIBN as initiator. The molecular weights and the chain transfer constant (C,) derived from a Mayo plot are given in Table 9.
Table 9: Molecular weights and conversions for vinyl acetate polymerizations carried out in the presence of 2-tosyl-3-(tosylmethyl)propene CTA Wt Cs Wt of Mn Mw/Mn of I
CTA polymer (mg) 0 3.9 1.4853 85,092 2.1 II
/'~~~H3 10.3 1.2977 43,794 2.1 20.3 1.0838 32,266 1.9 CH=-S~H; 40.0 0.9126 17,164 2.1 of From the results shown in Table 9, 2-tosyl-3-(tosylmethyl)propene exhibits excellent though mildly degradative chain transfer in vinyl acetate polymerization:
Throughout this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group s of integers.
It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as described without departing from the spirit or the scope of the invention, the present examples and specific details are, therefore, to be considered in all respects as illustrative of the invention and are in no way meant to be limitive.
1.2 g).
Example 4: Polymerization of hinyl Acetate by Feed Process A three-necked reactor was equipped with a reflux condenser and a pressure equalizing funnel with metering valve. The reactor was held under nitrogen positive pressure and the following ingredients were used.
Vinyl Acetate 50 ml Methanol 10 ml arf 2 CTA (Ia) 100 mg (Ex 4.1) or 505 mg (Ex 4. 2) AIBN 8.7 mg Methanol Sml Part 1 was charged to the reactor and heated to reflux (oil bath temperature was set at 80°C) under nitrogen atmosphere. When the temperature stabilized for 10 minutes, part 2 was charged to the reactor over 100 minutes via a pressure equalizing funnel with metering valve. Then the reaction mixture was held for further 3 hours (Example 4.1) or 24 hours (Example 4.2). The solvent and unreacted monomer were then distilled off. The results are summarized in Table 4 below. In the absence of CTA, the polymerization of vinyl acetate initiated by AIBN (total reaction time: two hours and forty minutes) in methanol gave polyvinyl acetate) with M" 131 380 and 34% conversion. The results in Table 4 below demonstrate that the molecular weight can be halved without decreasing conversion of monomer to polymer.
Table 4 ' Example CTA(Ia) Mn Ma, % Conv.
No.
4.1 100 mg 95 190 250 555 34.4 4.2 SOS mg 62 580 215 130 43.1 w0 97/13792 PCT/AU96/00622 Example 5: Preparation of Controlled Molecular Weight Poly(Yinyl Chloride) Using 2, 3 Dichloropropene (1a) Suspension polymerization of vinyl chloride was carried out using the following procedure.
S First, 25 L of water, 8.5 g of bis(4-t-butylcyclohexyl) peroxydica.rbonate, 40 mL of a suspending agent (4% Alcorex 72.5) and an appropriate amount of 2,3-dichloro-1-propene chain transfer agent (CTA, see Table 5) were charged in sequence into a 40 L
stainless-steel reactor and then the agitator was started at 300 rev/min. At this stage, the reactor was maintained under reduced pressure for a few minutes and then 3.15 Kg vinyl chloride monomer was charged to the reactor. The agitator speed was increased to 575 rev/min and the temperature of the mixture raised to SO°C. The polymerization was conducted at 50°C and a pressure of 690 kPa for 3.5 hours. The resulting product was separated by centrifuging, washed, dried and analyzed.
The conversion and molecular weight data are tabulated in the Table S.
Table S
Molecular weights and conversions for vinyl chloride polymerizations carried out in the presence of 2, 3 Dichloropropene (la) example 1C1'A~
LQ % Conv. M" Mw K value*
5.1 0 40.6 71,630 134,230 70.3 _ 5.2 0.2 30 65,870 137,880 68.5 5.3 1.0 30 41,420 90,530 50.2 * a measure of molecular weight from the equation:
75 KZxlO's leg 1~ _ - + K x 10-3 C
1 +l.SKcx 10-~
WO 97!13792 PCT/AU96/00622 Example 6: Preparation of Controlled Molecular Weight Olefin-Terminated Polymers of Vinyl Acetate Using 3-bromo-2-chloroprop-1-ene (I,fi ,~ nthesis of 3-bromo-2-chloroprop-1-ene (If!
A mixture of 2,3-dichloropropene (5.5g, 49.5 mmol), sodium bromide 5.16g) and ethyl bromide (37mL, 495 mmol) in DMF (60mL) was allowed to heat at 80°C for 27 hours.
After cooling to room temperature, the reaction mixture was diluted with saturated sodium chloride solution, and extracted three times with petroleum spirit 30-40°C. The combined organic layer was washed with water twice and then once with brine. After drying (anhydrous MgS04) and removing solvent on a rotary evaporator, the title compound (If) was obtained (2.47g, 32%) after vacuum distillation in a Kugelrohr apparatus (set at 70°C, 25mmHg). 1H-NMR (CDCl3) 8 (ppm): 4.09 (s, 2H, CHaBr); 5.40 and 5.59 (2s, 2H, vinylic-H).
Polvmerizations The polymerisations were carried out for one hour in sealed glass tubes in vacuo at 60°C
with AIBN in the manner of example 1. The molecular weights and the chain transfer constants (C$) derived from the Mayo plots are summarized in Table 6.
Table 6:
Molecular weight data and chain transfer constant for polymerization of vinyl acetate in the presence of (I,~
S CTA Wt of C Wt of M n Mw~
CTA polymer ~mg) CH -Br 0 28.7 1.7566 177,048 2.4 /
CHz-C 11.1 0.1620 3,251 1.9 \C1 ' 20.4 0.0857 1,631 1.6 40.2 0.0406 1,240 1.4 f E D.,1..~+..~e..,..
... __i__ , - , --,, - ---- --1»~ . ...,......, uuuiva..a iuvicl.u10.1 W Gt~tl6.
Example 7:
Preparation of Controlled Molecular Weight Styrene Butadiene Rubber (SBR) by Emulsion Polymerization using 2, 3-Dichloropropene (Ia) Emulsion polymerization of Styrene-Butadiene was carried out using the standard conditions for polymerization of Styrene-Butadiene which requires oxygen free reaction I S conditions in bottle reactors rotated in a polymerization bath at approximately 4S RPM and S' C.
The procedure was as follows:
The following were added to 2S0 ml bottle reactors fitted with butyl rubber serum-cap liners:
Reactor Charge Deionized Water 9gg Styrene 14. Sg Butadiene 3 S.Sg DRS 40 (surfactant) 0.6758 Westvaco 1480 (surfactant) 1.5758 KOH 0.308 Darvan WAQ ( surfactant) O.OSOg KCl O.15g EDTA bis-sodium salt O.OOSg Sodium Dithionite 0.01258 2,3 Dichloropropene (CTA) (1q) O.OSSg Initiator Solution Deionized Water 2g NAFE 0.01 g ' Sodium Formaldehyde Sulfoxylate O.OSg Cumene Hydroperoxide 0.0758 After the bottle reactors with reactants as shown above are brought to equilibrium in the 5°C bath, the Initiator solution is added via syringe. A sample is withdrawn from the reactor at about 40% monomer conversion and analyzed for molecular weight by Gel Permeation Chromatography (GPC). The sample is stopped from further polymerization by the addition of diethylhydroxyl-amine (DEHA).
After sampling, the polymerization of the remaining emulsion is continued until it is stopped by addition of DEHA when the monomer conversion was about 60%.
A control polymerization was run in the same fashion but without CTA added.
All polymers produced were analyzed by GPC for molecular weight.
The conversion and molecular weight data are tabulated in the Table 7.
w0 97/13792 PCT/AU96/00622 Table 7: ' Molecular weights arid conversions for SBR polymerizatiorzs carried out in the presence of 2, 3-Dichloropropene (Ia) S
Example [CTA] Conversion M #
n No. % (% ) 7.1 0.0 40 358,900 1,187,100 7.2 0.0 62 ** **
7.3 0.11 40 263,000 1,012,000 7.4 0.11 62 234,200 992,795 # Polystyrene equivalent number molecular weight.
** Too high molecular weight to filter and run on GPC
Example 8: Preparation of controlled molecular weight poly(methyl methacrylate) using 2-(chloromethyl)-3-tosylpropene (a) Synthesis of 2-(chloromethyl)-3-tosylpropene A solution of 2-(chloromethyl)-3-chloropropene (3.13g, 25mmo1) and sodium ~-toluenesulfmate (4.60g, 25mmol) in methanol (SOmL) was heated under reflux for 24 hours.
The solvent was evaporated on a rotary evaporator and the residue was extracted between dichloromethane and water. The organic layer was dried (anhydrous MgS04) and evaporated to give crude product (4.7g) which, after purification by column chromatography on a silica-gel column using ethyl acetate/n-hexane 1:9 as eluent, gave pure product (2.7g, 44% yield). 1H-NMR (CDCl3) b (ppm): 2.46 (s, 3H, CH3Ar); 3.92 (s, 2H, CHaSO~; 4.19 (s, 2H, CHZCI); 5.02 (s, 1H, vinylic-H); 5.45 (s, 1H, vinylic-H);
7.37 and 7.77 (2d, 4H, ArH).
r (~,l Polymerizations Polymerizations of methyl methacrylate were carried out in air-free sealed glass tubes at 60°C with AIBN as initiator. The molecular weights and the chain transfer constant (C,) derived from a Mayo plot are given in Table 8.
Table 8:
Molecular weights and conversions for methyl methacrylate polymeriZations carried out in the presence of 2-(chloromethyl)-3-tosylpropene CTA Wt Cs Wt of Mn M
of CTA polymer (mg) (g) (5.5) 0 0.05 0.18 198,402 1.9 II
10.1 0.18 172,385 1.7 ( ~Z= ~ 20.0 0.16 126,022 1.9 p 40.1 0.18 107.121 1.75 This particular transfer agent exhibits weak activity with MMA.
Example 9: Preparation of controlled molecular weight polyvinyl acetate) using (tosyl)-3-tosylmethylpropene (a) Synthesis of 2-fosyl-3(tosl~lmethyl)propene In a 100mL round bottomed flask, 2-(chloromethyl)-3-chloropropene (1.25g, lOmmol), sodium ~-toluenesulfinate (5.34g, 30mmo1) were mixed in methanol (SOmL) and the WO 97/13792 PC'~/AU96/00622 resulting mixture was heated under reflux. The reaction was followed by thin layer chromatography (silica-gel plate) with ethyl acetate/n-hexane 1:3 as solvent.
After 3.5 days, water (50 mL) was added and the mixture of products precipitated out as creamy solids (2.8g). The pure title compound was obtained (2.198, 60%) after column chromatography on a silica-gel column using ethyl acetateJn-hexane 2:3 as eluent. iH-NMR
(CDCl3) 8(ppm): 2.45 (s, 6H, 2xCH3Ar); 3.99 (s, 4H, 2xCH2S0~; 5.17 (s, 2H, vinylic-H);
7.34 and 7.72 (2d, 8H, ArH).
(b) Polymerizations Polymerizations of vinyl acetate were carried out in air-free sealed glass tubes at 60 ° C with AIBN as initiator. The molecular weights and the chain transfer constant (C,) derived from a Mayo plot are given in Table 9.
Table 9: Molecular weights and conversions for vinyl acetate polymerizations carried out in the presence of 2-tosyl-3-(tosylmethyl)propene CTA Wt Cs Wt of Mn Mw/Mn of I
CTA polymer (mg) 0 3.9 1.4853 85,092 2.1 II
/'~~~H3 10.3 1.2977 43,794 2.1 20.3 1.0838 32,266 1.9 CH=-S~H; 40.0 0.9126 17,164 2.1 of From the results shown in Table 9, 2-tosyl-3-(tosylmethyl)propene exhibits excellent though mildly degradative chain transfer in vinyl acetate polymerization:
Throughout this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group s of integers.
It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as described without departing from the spirit or the scope of the invention, the present examples and specific details are, therefore, to be considered in all respects as illustrative of the invention and are in no way meant to be limitive.
Claims (12)
1. A process for the production of lower molecular weight polymers by free radical-initiated polymerization of unsaturated species characterised by the use of an unsaturated compound of Formula I as a chain transfer agent:
wherein R1 and R2 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or heterocyclic ring, and halogen;
X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl, Y is selected from the group consisting of halogen, a polymer chain which has just been synthesized in the process, and CR3R4Z, Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl and optionally substituted arylsulfonyl;
provided that (i) when X is optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl, Y is not halogen, that (ii) when Y is halogen, X is chlorine or bromine, and one of R1 or R2 is substituted alkyl, the first carbon of the substituted alkyl does not have two substituents independently selected from carboxyl, ester, amide, nitrite and aryl, and that (iii) the compound of Formula I does not satisfy the general formula C4Br n H8-n where n is an integer in the range of 4 to 8.
wherein R1 and R2 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or heterocyclic ring, and halogen;
X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl, Y is selected from the group consisting of halogen, a polymer chain which has just been synthesized in the process, and CR3R4Z, Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl and optionally substituted arylsulfonyl;
provided that (i) when X is optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl, Y is not halogen, that (ii) when Y is halogen, X is chlorine or bromine, and one of R1 or R2 is substituted alkyl, the first carbon of the substituted alkyl does not have two substituents independently selected from carboxyl, ester, amide, nitrite and aryl, and that (iii) the compound of Formula I does not satisfy the general formula C4Br n H8-n where n is an integer in the range of 4 to 8.
2. A process according to claim 1 wherein R1 and R2 are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, phenyl, biphenyl, naphthyl, chlorine and fluorine.
3. A process according to claim 1 wherein R1 and R2 are independently selected from hydrogen, methyl, phenyl, chlorine and fluorine.
4. A process according to claim 1 wherein X is chlorine or bromine.
5. A process according to claim 1 wherein X is alkylsulfonyl or arylsulfonyl.
6. A process according to claim 5 wherein X is p-toluenesulfonyl, methanesulfonyl, trifluoromethanesulfonyl or benzenesulfonyl.
7. A process according to claim 1 wherein Y is halogen.
8. A process according to claim 1 wherein Y is CR3R4Z and R3, R4 and Z have the meanings defined in claim 1.
9. A process for preparing an A-B type block copolymer by free radical-initiated polymerization of a first unsaturated species in the presence of a first chain transfer agent of Formula I:
wherein R1 and R2 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or aromatic ring, and halogen;
X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl and optionally substituted arylsulfonyl;
Y is CR3R4Z, wherein R3 and R4 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or aromatic ring, and halogen; and Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl; provided that R1 and R2 are both hydrogen and/or R3 and R4 are both hydrogen;
to produce a second chain transfer agent of Formula I wherein Y is the just synthesized polymer chain, and polymerizing a second unsaturated species in the presence of the second chain transfer agent to produce an A-B type block copolymer of said first and second unsaturated species.
wherein R1 and R2 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or aromatic ring, and halogen;
X is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl and optionally substituted arylsulfonyl;
Y is CR3R4Z, wherein R3 and R4 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted saturated or aromatic carbocyclic or aromatic ring, and halogen; and Z is selected from the group consisting of chlorine, bromine, optionally substituted alkylsulfonyl, and optionally substituted arylsulfonyl; provided that R1 and R2 are both hydrogen and/or R3 and R4 are both hydrogen;
to produce a second chain transfer agent of Formula I wherein Y is the just synthesized polymer chain, and polymerizing a second unsaturated species in the presence of the second chain transfer agent to produce an A-B type block copolymer of said first and second unsaturated species.
10. A process according to claim 1 wherein the compound of Formula I is used in an amount of from 0.01 to 30 mole percent based on total monomer.
11. A process according to claim 10 wherein said compound of Formula I is used in an amount of 0.1 to 10 mole percent.
12. A process according to claim 1 wherein the compound of Formula I is selected from the group consisting of 2,3-dichloropropene, 3-chloro-2-chloromethyl-1-propene, 2,3-dibromopropene, 3-bromo-2-bromomethyl-1-propene, 2-bromo-3-chloropropene, 3-bromo-2-chloropropene, 3-chloro-2-fluoropropene, 3-bromo-2-fluoropropene, 2-(chloromethyl)-3-tosylpropene and 3-tosyl-2-(tosylmethyl)propene.
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| AUPN5855A AUPN585595A0 (en) | 1995-10-06 | 1995-10-06 | Control of molecular weight and end-group functionality in polymers |
| PCT/AU1996/000622 WO1997013792A1 (en) | 1995-10-06 | 1996-10-04 | Control of molecular weight and end-group functionality in polymers |
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| WO1998003556A1 (en) * | 1996-07-18 | 1998-01-29 | The Dow Chemical Company | Production of branched polymers |
| JP3739195B2 (en) * | 1997-11-17 | 2006-01-25 | 積水化学工業株式会社 | Method for producing polyvinyl alcohol resin |
| PT1062248E (en) * | 1998-03-12 | 2004-10-29 | Lucite Int Uk Ltd | POLYMER COMPOSITION |
| JP4632332B2 (en) * | 1998-12-18 | 2011-02-16 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing high molecular weight reaction product |
| ATE273325T1 (en) * | 1998-12-23 | 2004-08-15 | Basf Coatings Ag | COATING AGENT |
| US6444757B1 (en) * | 1999-06-11 | 2002-09-03 | Lord Corporation | Trifunctional olefinic-capped polymers and compositions that include such polymers |
| DE19930066A1 (en) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Color and / or effect multi-layer coating, process for their preparation and their use |
| DE19930067A1 (en) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Coating material and its use for the production of filler layers and stone chip protection primers |
| DE19930665A1 (en) | 1999-07-02 | 2001-01-11 | Basf Coatings Ag | Basecoat and its use for the production of color and / or effect basecoats and multi-layer coating |
| DE19930664A1 (en) | 1999-07-02 | 2001-01-11 | Basf Coatings Ag | Clear varnish and its use for the production of clear varnishes and color and / or effect multilayer varnishes |
| DE19959923A1 (en) | 1999-12-11 | 2001-06-28 | Basf Coatings Ag | Aqueous primary dispersions and coating materials, processes for their preparation and their use |
| DE19959927A1 (en) | 1999-12-11 | 2002-02-07 | Basf Coatings Ag | Aqueous primary dispersions and coating materials, processes for their preparation and their use |
| DE19961040A1 (en) * | 1999-12-16 | 2001-06-21 | Basf Ag | Thermoplastic molding compounds with improved processing behavior based on polyarylene ether sulfones and polyamides |
| DE10005819A1 (en) | 2000-02-10 | 2001-08-23 | Basf Coatings Ag | Aqueous primary dispersions, processes for their preparation and their use |
| DE10018078A1 (en) * | 2000-04-12 | 2001-11-08 | Basf Coatings Ag | Molding compositions and process for the production of moldings |
| DE10018601A1 (en) * | 2000-04-14 | 2001-10-25 | Basf Coatings Ag | Aqueous primary dispersion and coating agent useful in motor vehicle manufacture, is prepared by radical (co)polymerization of monomers dispersed in an aqueous dispersion of the cross-linking agent |
| DE10029695A1 (en) * | 2000-06-16 | 2001-12-20 | Basf Ag | Reaction product from monomer and radical-stabilizing compound is useful as emulsifier or dispersant, or as macroinitiator for preparation of polymers |
| DE10048258B4 (en) | 2000-09-29 | 2004-08-19 | Byk-Chemie Gmbh | Leveling agent for surface coatings |
| US7345127B2 (en) | 2001-03-23 | 2008-03-18 | University Of Pennsylvania | Living radical polymerization of halogen-containing and acrylic monomers and the formation of block copolymers therefrom |
| US6911515B2 (en) | 2001-03-23 | 2005-06-28 | University Of Pennsylvania | Aqueous room temperature living radical polymerization of vinyl halides |
| DE10126651A1 (en) * | 2001-06-01 | 2002-12-12 | Basf Coatings Ag | Use of copolymers with diphenylethylene units as emulsifiers for the production of powder slurry and coating powder for use in coating materials, adhesives and sealants, e.g. for painting cars |
| DE10126650B4 (en) * | 2001-06-01 | 2005-08-18 | Basf Coatings Ag | Functional organic powders, process for their preparation and their use |
| WO2003002621A1 (en) | 2001-06-27 | 2003-01-09 | University Of Pennsylvania | Radical polymerization of vinyl halide |
| DE10206983A1 (en) * | 2002-02-20 | 2003-09-04 | Basf Coatings Ag | Process for the preparation of aqueous dispersions of block copolymers |
| US7226957B1 (en) * | 2003-11-03 | 2007-06-05 | University Of Iowa Research Foundation | Method for producing polymers with controlled molecular weight and end group functionality using photopolymerization in microemulsions |
| JP2006063092A (en) * | 2004-07-29 | 2006-03-09 | Dow Corning Toray Co Ltd | Curable organopolysiloxane composition, its curing method, optical semiconductor device and adhesion promoter |
| EP2166026B1 (en) * | 2007-07-11 | 2014-01-15 | Asahi Glass Company, Limited | Method for production of water-repellant/oil-repellant composition, and article |
| KR20140119116A (en) | 2012-01-18 | 2014-10-08 | 아이오와 스테이트 유니버시티 리서치 파운데이션, 인코퍼레이티드 | Thermoplastic elastomers via atom transfer radical polymerization of plant oil |
| JP6020876B2 (en) * | 2012-03-13 | 2016-11-02 | 川崎化成工業株式会社 | Chain transfer agent having condensed polycyclic aromatic skeleton, polymer having condensed polycyclic aromatic skeleton, and method for producing polymer |
| JP2016528306A (en) | 2013-05-20 | 2016-09-15 | アイオワ、ステイト、ユニバーシティー、リサーチ、ファウンデーション、インコーポレイテッドＩｏｗａ Ｓｔａｔｅ Ｕｎｉｖｅｒｓｉｔｙ Ｒｅｓｅａｒｃｈ Ｆｏｕｎｄａｔｉｏｎ，Ｉｎｃ． | Thermoplastic elastomers via reversible addition-fragmentation chain transfer polymerization of triglycerides |
| CN108484820A (en) * | 2018-03-06 | 2018-09-04 | 中国林业科学研究院林产化学工业研究所 | A kind of synthetic method of novel acrylic ester lotion |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4052546A (en) * | 1976-10-29 | 1977-10-04 | Tenneco Chemicals, Inc. | Process for the production of vinyl halide polymers |
| AU605534B2 (en) | 1986-12-05 | 1991-01-17 | Commonwealth Scientific And Industrial Research Organisation | Control of molecular weight and end group functionality of polymers |
| US5932675A (en) * | 1989-06-05 | 1999-08-03 | Commonwealth Scientific And Industrial Research Organisation | Free-radical chain transfer polymerization process |
| AU6616990A (en) | 1989-11-01 | 1991-05-31 | Commonwealth Scientific And Industrial Research Organisation | Control of molecular weight and end group functionality in polymers using unsaturated peroxy compounds as chain transfer agents |
| ES2284159T3 (en) * | 1992-05-01 | 2007-11-01 | E.I. Du Pont De Nemours And Company | PREPARATION OF RETICULABLE POLYMERS USING MACROMONOMERS AS CHAIN TRANSFER AGENTS. |
| US5264530A (en) * | 1992-05-01 | 1993-11-23 | E. I. Du Pont De Nemours And Company | Process of polymerization in an aqueous system |
| IL111484A (en) * | 1993-11-03 | 2001-06-14 | Commw Scient Ind Res Org | Polymerization process using allylic chain transfer agents for molecular weight control, the polymers obtained thereby and certain novel allylic compounds |
| AU688403B2 (en) * | 1993-11-03 | 1998-03-12 | Commonwealth Scientific And Industrial Research Organisation | Allylic chain transfer agents |
-
1995
- 1995-10-06 AU AUPN5855A patent/AUPN585595A0/en not_active Abandoned
-
1996
- 1996-03-10 IN IN1750CA1996 patent/IN192281B/en unknown
- 1996-10-02 TW TW085112018A patent/TW410229B/en active
- 1996-10-04 ES ES96931683T patent/ES2170262T3/en not_active Expired - Lifetime
- 1996-10-04 PL PL96326029A patent/PL326029A1/en unknown
- 1996-10-04 WO PCT/AU1996/000622 patent/WO1997013792A1/en active IP Right Grant
- 1996-10-04 NZ NZ318731A patent/NZ318731A/en unknown
- 1996-10-04 US US09/066,362 patent/US6235857B1/en not_active Expired - Fee Related
- 1996-10-04 DE DE69617973T patent/DE69617973T2/en not_active Expired - Fee Related
- 1996-10-04 DK DK96931683T patent/DK0853634T3/en active
- 1996-10-04 BR BR9611112A patent/BR9611112A/en not_active IP Right Cessation
- 1996-10-04 KR KR10-1998-0702461A patent/KR100412294B1/en not_active IP Right Cessation
- 1996-10-04 CA CA002231398A patent/CA2231398C/en not_active Expired - Fee Related
- 1996-10-04 CN CN96197440A patent/CN1116308C/en not_active Expired - Fee Related
- 1996-10-04 EP EP96931683A patent/EP0853634B1/en not_active Expired - Lifetime
- 1996-10-04 JP JP51456397A patent/JP3624259B2/en not_active Expired - Fee Related
Also Published As
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|---|---|
| IN192281B (en) | 2004-03-27 |
| AUPN585595A0 (en) | 1995-11-02 |
| DE69617973T2 (en) | 2002-08-01 |
| PL326029A1 (en) | 1998-08-17 |
| DK0853634T3 (en) | 2002-04-08 |
| JPH11513429A (en) | 1999-11-16 |
| KR100412294B1 (en) | 2005-01-15 |
| CA2231398A1 (en) | 1997-04-17 |
| EP0853634B1 (en) | 2001-12-12 |
| EP0853634A4 (en) | 1998-09-30 |
| CN1198749A (en) | 1998-11-11 |
| DE69617973D1 (en) | 2002-01-24 |
| EP0853634A1 (en) | 1998-07-22 |
| US6235857B1 (en) | 2001-05-22 |
| KR19990063986A (en) | 1999-07-26 |
| ES2170262T3 (en) | 2002-08-01 |
| NZ318731A (en) | 2000-01-28 |
| BR9611112A (en) | 1999-07-13 |
| TW410229B (en) | 2000-11-01 |
| CN1116308C (en) | 2003-07-30 |
| JP3624259B2 (en) | 2005-03-02 |
| WO1997013792A1 (en) | 1997-04-17 |
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