CA2246416A1 - Branched polymer synthesis - Google Patents
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- CA2246416A1 CA2246416A1 CA002246416A CA2246416A CA2246416A1 CA 2246416 A1 CA2246416 A1 CA 2246416A1 CA 002246416 A CA002246416 A CA 002246416A CA 2246416 A CA2246416 A CA 2246416A CA 2246416 A1 CA2246416 A1 CA 2246416A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
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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
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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
Abstract
This invention relates to a process for the synthesis of addition polymers containing branches upon branches and having a polymerizable olefin end group by a convenient one-pot copolymerization of selected vinyl monomers with chain polymerization initiators and a method to provide olefin end groups by chain transfer or termination agents; and polymers produced thereby.
Description
TIT~
BRANCHED POLYMER SYNTHESIS
Precise macromolecular engineering using commodity monomers is S becoming a major trend in polymer technology to satisfy the clem~n-i for newproperties, improved cost effeetiveness, ecology and quality. Functional polymers with low molecular weight, low polydispersity, compact, branched struetures and t~rmin~lly loeated reaetive groups are expeeted to exhibit superior p~.rc,~ ee/eost eharaeteristies, by virtue of lower inherent viseosity and higher reactivity vs. eonventional linear statistieal eopolymers.
The t~rmin~lly funetional branehed polymers appear to be ultimate reactive substrates for networks, because the braneh points can substitute for asignificant portion of expensive reaetive groups and provide a ~etter eontroll of the reaetive groups distribution. Partieularly polymers having large numbers of short br~nehec below eritieal moleeular weight are unlikely to form any ~nt~ngl~ nent~ and should exhibit low inherent viseosity and good flow even in eoncellL~dLed solutions.
Conventional teehniques for sythe~i7in~ well defined branehed polymers require expensive mul*~t~p proeesses involving isolation of reaetive int~rmPtli~l.laclolllonomers. The macromonomers have polymerizable end groups, which are usually introdueed using funetional initiator, termin~ting or ehain transferagent. Well defined branehed polymers are prepared by the macromonomer homopolymerization or copolymerization with suitable low moleeular weight eomonomer seleeted based on known reaetivity ratios.
U.S. 4,680,352 describes molecular weight reduction and maeromonomer (polymers or copolymers with unsaturated end-groups) synthesis in copolymen7~tions with acrylates and styrene with various Co(II) complexes.
J. Antonelli, et. al., U. S. 5,362, 813 and C. Berge, et al., U. S. 5,362,826 diselose the p~ ~dLion of maeromonomers by radical addition-fr~men~tion processes and the copolymerization of maeromonomers. Branehed structures were not well charaeterized and the reincorporation of the branched macromonomers into more complex structures was not considered.
Dendrimers or h~ ui~lched polymers prepared using e.Ypensive. special multifunctional monomers or expensive multistep methods re~uiring repetitive isolation of the reactive interrne~ st-f c have been reviewed by J.C.Salamone, ed., Polymeric ~atf'rt~l~ Encyclopedia, Vol.5 (1996).
The references cited above cover the copolymeri_ation of vinyl monomers in the presence of chain transfer reagents, but do not disclose synthetic conditions for production of macromonomers or polymers cont~;ning branches upon branches.
SUMMARY OF TRrF TNVh,NTION
This invention relates to a general process for the synthesis of arlrlit;on polymers contz-ining branches upon hr~nrhf s and having a polymerizable olefin end group by a convenient one-pot polymerization of selected vinyl monomers with chain polymeri_ation initiators and a method to provide olefin end groups by chain transfer or tt~rrnin .tion agents. The pol~.n~,l;~lion is carried out in such a manner that chain transfer occurs frequently and each chain transfer event tf - ~JI;IIi~ that particular polymer chain with termin~l polymerizable olefinicfunctionality. Subsequent reincorporation of the polymer chains produced early in the reaction leads to br ~nrhing of subsequently-fo~med polymer chains which aretf ~ minate~l with polym~ i7~hle olefinic functionality. Subsequent reincorporation of the branched polymer chains leads to subsequently-forrned polymer chains cont~inin~ branches-upon-branches which are t-f nnin~t~d with polymerizable olefinic functionality. Spontaneous repetition of the process leads to highly branrh~cl or hyperbranched products still retaining termini with polymerizable olefinic functionality.
This invention concems an improved process for the free-radical polymerization of at least one unsaturated vinylic monomer to form a polymer whose molecular architecture includes branches upon branches and a polymerizable vinyl-terrnin~te(l end group, comprising contacting, in the ~scn~eof a free-radical initiator:
(i) one or more vinylic monomers having the formula CH2=CYZ and (ii) a chain transfer agent of formula CH2=CQ-CH2-X, wherein:
Y is selected from the group consisting of OR, O2CR, halogen, CO~H, COR, CO~R, CN, CONH2, CONHR. CONR, and R';
Z is selected H, CH3, or CH2OH;
R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted andunsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or dirr~ L and selected from the group consisting ofcarboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, ~ILilll~Ll,y amino, secon-i~ry amino, tertiary arnino, isocyanato, sulfonic acid and halogen, and the number of carbons in said alkyl groups is from 1 to 12; and R' is selected from the aromatic group con~i~ting of substituted and l-n~bstituted aryl, s~ and un~ul,~.liLu~ed heteroaryl, the snhstihlçnt~ being the same or different and selected from the group con~i~ting of carboxylic acid,carboxy}ic ester, epoxy, hydroxyl, alkoxy, ~lihll~y amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, s~bstitllt~d and unsubstituted alkyl,sllbstit-lt.od and L~ ub~liLuL~d aryl, ~ub~LiluLed and ull~ub~LiLuLed olefin andhalogen;
X is selected from -(CUY-CH23n-Z', S(O)R, S(O)2R, SnR3, halogen, R2 and R3;
U is selected from H and R;
Q is selected from Y, or in the case where X is halogen, Y and H;
Z' is selected from H, SRI, S(O~R, S(O)2R, R2 and R3;
nis2 1;
R is selected from the group substituted and unsubstituted alkyl, aryl.
aralkyl, alkaryl and org~nc)~ilicon groups wherein the snkstitllent(s~ are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
Rlis selected from the group H, substituted and unsubstituted alkyl. aryl, aralkyl, alkaryl and org~nr ~ilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl. alkoxy, amino and halogen;
R2 is selected from the group free radical initiator-derived fr~gment.~ of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, S alkoxyalkyl, alkoxyaryl, sulfate groups wherein the sub.lil~ (s) are independently selected from R, ORI, 07CR, halogen, CO2H and salts thereof, CO2R, CN, CONH2, CO2NHR, CONR2;
R3 is st?lected from the group free radical initiator-derived fr~gme~t~ of iL.,~A and lln.cllhst;tll~Pd alkyl, cycloalkyl, aryl, aralkyl, alkarvl, organosilyl, alkoxyalkyl, alkoxyary}, and P(O)R2 groups wherein the substituent(s) are independently selected from R, ORI, 02CR, halogen, CO2H and salts thereof, CO2R, CN, CON~2, CO2NHR, CONR2;
wherein the improvement comprises obtaining higher yields of polymer having the branch-upon-branch ~uellile-;LIlre and polymerizable vinylic chain termini, and a higher density of br~nch~os upon br~nl~h~ in that polymer by optimi7in~ the polymen7~t;0n in the following way: select step III and at least one of I; II; I and IV; and II and IV from steps:
I - decleasillg reactivity ratios of (i) and the resulting vinylic-term;n~t~d macromonomers and polymers toward O;
II - selecting the ratio of (i?/(ii) between 2 and 100, dependent on the values of 1, III and IV;
III - hlclea~ g the conversion of (i) and (;i) from 80% toward 100 %;
IV - i~ ea~hlg the temperature from 50~ toward 150~C.
Based on the disclosure and Examples presented herein, one skilled in the art will be readily able to select the optimum ratio of (i)/(ii) for any given class of monomer(s) and values of (i), (iii) and (iv) with minimum experimentation. One skilled in the art v~rill also be able to select the a~ l;ate chain transfer agent for the monomer(s~ being polym~ri7~ by reference to the well-known reactivity ratios of said chain transfier agents and monomer(s).
This invention further concerns the product of the above reaction which is composed primarily of a polymer having a branch-upon-branch structure and a polymerizable olefinic end group, having the structure:
X--CH2--C~H2--~ C~--f ~_C
\ /n \ /m \ Ip where B' =
X--CH2--C~H2--C~ Cl~z ~n \ /m \ /P
B" = X, B', H, CH3, CH2CHR'CH3, or CH2CMeR2CH3, n= 1-20,m=0-5,p=0-20;n+m+p>2;
and if m >1, then the m insertions are not consecutive. X, Y, Z, Rl and R2 are as earlier ~l~fine~l l)li',T~TT,Ti',T) DF~CRTPTION
We have discovered a general process for the synthesis of addition polymers co~ ;..i..g branches upon branches and having apolymerizable vinylic end group by a convenient one-pot polymeri_ation of selected vinyl monomers with chain polymerization initiators and a method to provide olefin end groups by 20 chain transfer or t~ ion agents. The polymeri7~tion is carried out in such a manner that chain transfer occurs frequently and that each chain transfer event terminates that particular polymer chain termin~tecl with polymerizable olefinicfunctionality. The process is shown in Scheme 1.
Scheme 1.
5 Step t. rO-, ~n of llncar ~.,a~",.onaa._.s 1 r~ tiO., UNsA~ EDuMc~NoMER Chain Transfer or Tt~ n P~ liu-~/
UM ChainTransfer Step ~r.,- ~ nofprimary~ ed.. a~,.ull.unu.. _.a 2 orTe~.~l k 1 Stcp3. F~- ~- hof branch-upon-branch .. ~c~o.. ~u.,l~mers 3 Pol~ L~ ùn/
UM ChalnTransfer or Tennination etc Sul~se~lu~.ll r~,hlcc..~oldlion of the polymer chains produced early in the reaction 25 leads to l,.~...fh;..~ of subsequently-forrned polymer chains which are terrnin~tt?d with poly~ .,~l,le olefinic fi-n~tion~1ity. Subsequent reincorporation of the br~n~ ~d polymer chains leads to ~l,se-luently-formed palymer chains cont~inin branches-upon-l,.dllches which are t~rrnin~ted with polymerizab}e olefinic fi~nctionality. Spontaneous repetition of the process leads to highly branched or 30 hyp~blallched products still ret~ininp~ terrnini with polymerizable olefinic functionality.
The polymers made by the present process are useful in a wide variety of co~tings Other potential uses can include cast, blown, spun or sprayed applications in fiber, film, sheet, composite materials, multilayer co~t;ng~, photopolymeri_able materials, photoresists, surface act;ve agents, dispersants.
5 adhesives, adhesion promoters, coupling agents, commpatibilizers and others.
End products taking advantage of available characteristics can include, for example, automotive and arçhit~-ctl~ral coatings or fini~hç~, including high solids, aqueous or solvent based fini.~hes Polymers, such as those produced in this invention, would find use in, for example, structured polymers for use in pigment 1 0 dis~
In a l),cr~.ied process the free-radical initiator is selected from azo initiators, typical examples of which include: 2,2'-a_obis(isobutyronitrile), VAZO-88 = l,1'-~obis(cyclohex~ne-l-c~l,ollik;le) (DuPont Co., Wilmington, DE) VR-110 = 2,2'-azobis(2,4,4-trimt;Lllyl~el-la..e) (Wako Pure Chemir~l Industries, Ltd., Osaka, Japan) Chain transfer reagents, CH2=CQ-CH2-X, can be based upon vinylidene macromonomers ~c~ed by several methods. A good example is the methyl methacrylate trimer, CH2=C(CO2Me)-CH2-CMe(CO2Me)-C~2-CMe(CO2Me)-CH3. These radical addition-fr~gment~tion chain transfer agents have been 2~ reviewed by E. Ri zardo, et al., Macromol. Symp. 98, 101 (1995).
Other organic chain transfer reagents include allylic sulfides, sulfones, bromides, phosphonates, sf~nnRnes, vinylidene termin~fe~1 methacrylic oligomers,a-methyl styrene dimer and related compounds. Preferred chain transfer agents and polym~ i7~hle interme~i~te macromonomers exhibit dual reactivity, in that 25 they can both undergo copolymerization or homopolymerization as well as promote colllpclilive chain transfer through the addition-elimination process.
Substituent Q of the chain transfer reagent is chosen to convey the a~lo~liate reactivity of the olefinic group in radical polymerization of the desired monomer~s) under polymerization conditions. The substituents Q and X can also 30 be chosen so as to introduce any required end-group functionality into the polymer. Therefore using functional chain transfer agent (iii) can be a preferedmethod. These end groups can be the same or different and can be chosen such that the final polymer can be telechelic. Suitable end groups are particularly those compatible with free radical polymerization and include epoxy, hydroxyl, S carboxyl, silyl.
The process can be potentially con~ te~ by bulk, solution, suspension or emulsion polymerization using batch or preferably starved feed reactor, which offers better process control.
The treelike branched polymers are formed by in situ generation and 10 copolym~-i7~tion of first linear and subsequently increasingly branched macromonomers through the polymerizable olefin group. The method was demonstrated by model kinetic studies of monomer, chain transfer agent (CTA) conversions, polymer molecular weight increase combined with qll~ntit~tive end group and br~n..hing characteri_ation when reacting vinylidene MMA-kimer used 15 as a CTA and butyl acrylate ~BA) in a starved-feed reactor. Macromolecules typically with 2 to 30 branches each c~ 5 to 20 monomers were prepared, branch length being primarily controlled by the monomer/chain transfer agent ratio, conversion and to some extend by t~ lpc;ldlul~.
A chain polymeri7~tion is conkolled by a chain transfer step so as to 20 provide a polymeri7~hle olefin end group (Scheme 1~. The branch-upon-branch ~l~u~ e is buik by in situ generation and copolylllc,i~Lion of linear and subsequently increasingly branched macromonomers through the polymerizable olefin group.
That monomer copolymeri7~hility is primarily determined by the steric 25 and eleckonic properties is well doc1-mentecl in the art. The chain process can involve either one or several different comonomers. Typical monomers include acrylates, methacrylates, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, a-methylstyrene, halogenated olefins, vinyl esters, butalso can include N-vinyl carbazole, N-vinyl pyrrolidone,and dienes such as 30 isoprene, and chloroprene.
Quantitative NMR analysis of the products, particularly end group structure and br~nching, combined with oligomer analvsis by MALDI mass CA 022464l6 l998-07-3l ~.~e~ osco~ show that conventional radical termination and chain transfer processes can be effectively suppressed under these conditions, when acrylates (or styrene) are copolymerized with the vinylidene macromonomer/chain transfer agent . The polymer molecular weight and end group structure are predominantly controlled by the ~-scission chain transfer. High conversions (usually 80-90 %) of the vinylidene end group are predominantly achieved by the incorporation, i.e., copolymeri7~tion leading to branches. The data are consistent with a mech~ni~m, in which the initially forrned branched macromolecules receive predominantly thevinylidene end group through the ~-scission chain transfer. Having a reactive vinylidene end group allows the singly-branched macromolecules to participate inanalogous subsequent (secondary) copolymerization steps leading eventually to even more branched structures, which could be called branch-upon-branch polymers.
Formation of branch-upon-branch ~ul;Lul~s is indicated by the signifir~nt } 5 ir~ ,ase in the polymer molecular weight and in the number of branches per polymer molecule that occurs even at nearly complete conversion of the vinylidene (MMA)3=, which was used as a chain transfer agent and model macromonomer and at high acrylate monomer conversions. The development of ~'h~r~ ion methods for branched polymer formation from vinylidene macromonomers by NMR, SEC, GC, MALDI mass spectroscopy was ecst-nti~l for developing and CO~ 1 ion of this method of mal~ing branch-upon-branch structures, see E. McCord, et al., ACS Polymer Prep. 36 (2), 106 (1995).
Br~nçhing density ~stim~tecl from the ratio of grafting to ,~-scission is primarily clet~TTnin~(i by the BA/chain transfer agent ratio, conversion and to some extend by te~ )eld~ in the range 60 to 100 ~C. Under standard conditions, one MMA-trimer branch occurs per 8 to 16 BA comonomers con~llme-l, which corresponds to l 000 - 2,000 molecular weight of BA segment per one ~ranch and is desirably below an entanglement length.
The copolymers were characterized by lH and 13C NMR, by conventional SEC using RI detector vs. PMMA standards and compared with data obtained using universal calibration in THF and the light-scattering weight-average molecular weights. Under typical radical copolYmerization conditions in starved CA 02246416 l99X-07-31 feed reactor used in these studies, about a I 0-fold molar excess of acrylate comonomer over mPth~rrylate vinylidene macromonomer is required to achieve acceptable yield (> 10 %) and a significant number (>5) of branches per macromolecule. The number of 5 branches per molecule is a min;murn (per 5 definition) for branch-upon-branch structures.
Kinetic data at early and int~rme~ t~ conversions showed as expected that ~-scission is favored over incorporation by higher L~ aLulcs. At almost complete vinylidene group collvcL~iion, the effect of tcLllpcidluLe on the overall ratio of incorporation to ~-scission was found to be small. This is evidently due to 10 somewhat higher activation energy of the competing ~-scission vs. the incol~olaLion and due to the fact that incorporation is a major merh~ni~m of thevinylidene group con~ Lion.
Pl~r~ cd monomers are:
methyl acrylate, 15 ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers3, 2-ethylhexyl acrylate, isobornyl acrylate, 20 acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, glycidyl acrylate, 25 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), diethylaminoethyl acrylate, triethyleneglycol acrylate.
30 N-tert-butyl acrylamide, N-n-butyi acrylamide, N-methyl-ol acrylamide, CA 022464l6 l998-07-3l N-ethyl-ol acrylamide, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, 5 Aimçthoxymethylsilylpropyl acrylate, diethoxymethylsilylpLoyyl acrylate, dibutoxymethylsilylpropyl acrylate, diisoyuoyo~ymet-h-ylsilylpropyl acrylate, ~iim~thoxysilylyruyyl acrylate, 10 diethoxysilylyl()yyl acrylate, dibutoxysilylylo~yl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, vinyl propionate, 15 vinyl butyrate, vinyl bt?n7.0ate, vinyl chloride, vinyl fluoride, vinyl bromide.
20 methyl methacrylate, ethyl meth~r.rylate, propyl meth~rrylate (all isomers), butyl m~th~rrylate (all isomers), 2-ethylhexyl methacrylate, 2~ isobornyl meth~r.rylate, methacrylic acid, benzyl methacrylate, - phenyl melllacl ylate, methacrylonitrile, 30 alpha methyl styrene, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethyl-silylpropylm~,acl ylate, dibutoxymethylsilylpropyl methacrylate, 5 diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibuLu2~y~ilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, isoE~lo~ yl ~)UIyld~
isolJIo~u~llyl acetate, iS~ Io~ yl b~n7n~tf iSO~O,,u~llyl chlor~
iso~Lopcllyl fluoride, 15 i~o~lo~ yl bromide itaconic acid itaconic anhydride d~ llyl itC~n:~t~, methyl itaconate 20 N-tert-butyl m~th~r.rylamide, N-n-butyl methacrylamide, N-methyl-ol methacrylamide, N-ethyl-ol methacrylamide, iso~ .,ylbenzoic acid (all isomers), 25 diethylamino ~lrh~nlethylstyrene (all isomers), para-methyl-alpha-methylstyrene (all isomers), diisopropenylbenzene (all isomers), isoL~ enylbenzene sulfonic acid (all isomers), methyl 2-hydroxymethylacrylate, 30 ethyl 2-hydroxymethylacrylate, propyl 2-hydroxymethylacrylate (all isomers), butyl 2-hydroxymethylacrylate (all isomers), 2-ethylhexyl 2-hydroxymethylacrylate.
isobornyl 2-hydroxymethylacrylate, styrene, vinyl benzoic acid (all isomers), S diethylamino styrene (all isomers), para-methylstyrene (all isomers), divinylbenzene ~all isomers), and vinyl benzene sulfonic acid (all isomers).
~X~1~1PT,F.C~
F,~r~ples 1-15:
P~ lion of Br~nch-Upon-Rr~nch Poly(butyl acrylates) U~in,p Meth~yl Meth~ylate Vin~ lene Trimer (MM~.)3_ 15~ Ch~in Tr~n~fer A~ent ~n~l Macromonorner This procedure illustrates the plepa alion, analysis and proof of the branch-upon-branch polymer archit~c~lre in which there are at least 5 branches in a starved feed reactor by a multi step/one pot process. Conditions of the branch-20 upon-branch ~llu;Lu~e formation are identified from the effects of L~m~ dl~e,monomer, chain transfer agent and initiator concentrations and conversion on thepolymer structure. The broken line in each of the following Tables will indicatewhere significant levels of branch-upon-branch polymers are produced.
The polymers of this invention with the most desirable plu~ Lies are those 25 having at least 10%, more preferably at least 25%, and most preferably above 50%, branch upon branch architecture.
WO 97131031 rCT/US97/02913 EXAI~IPLE I
Polymerization of Butyl Acrylate w~th Vinylidene l~Iethyt Methacrylate-Trimer as a Chain Transfer Agent and Macromonomer at 70~C.
5 Part r~r~ nt Amol-nt Toluene 8 g Decane 1 g (MM~)3=
II Toluene 25 g 2,2'-a7obis(2-methylbl-t~nP.nitrile) 1 g III Butyl acry}ate 32 g Part I was charged into the reactor equipped with stirrer, reflux condenser, thermocouple, and nitrogen positive ~ ule, and heated to 70~C. Part II and III
were fed con.,ul.c,,,lly into the reactor over 150 and 120 minllte~, respectively.
After completing the addition of Part II, the reactor collL~llL~ were held at 80~C for an additional 60 minllte~ The copolymeri7~tion kinetics have been followed by gas chromatography, NMR and GPC. ~5 g samples of the reaction mixture were withdrawn at 20 min. intervals followed by GC ~ltotennin~tion of the BA and 20 vinylidene MMA-trimer conc~l.LldLions. Volatiles were stripped on high vacuumfor several hours and the oligomers/polymers were analyzed by NMR and GPC.
Decane was used as an internal standard and molar response factors were d~t-ormin-ocl using ~ Lul~s of known composition cont~ining SCT MMA-trimer, BA and decane. The kinetic data are shown in Table 1. Polymer composition was 25 followed by Matrix Assisted Laser Desorption lonization (MALDl) Mass Spectroscopy. Polymer molecular weight was measured by S~C and viscometry.
Structure of both polymers, including br~nching density and end groups, was characterized by lH and ~3C NMR.
Table I
Time CTA' Polymer Composition No of Polymer (min) conv. (mole%) Br. Per ~d) (%)(MMA)3 MMA= E~A Mn Mn Mnd) PDd) Mne) (dL/g) 23 24.839.318.7 42.0 ~.1 1200 1100 43 25.139.318.0 42.8 2.2 1300 1600 63 36.419.911.4 68.7 1.7 1600 2100 83 48.410.7 7.8 81.5 1.4 2100 2600 103 63.4 8.2 6.1 ~5.7 1.4 2500 3100 2400 2.4 0.055 120 75.5 7.3 3.8 88.9 1.9 3900 4300 3800 3.2 0.~61 140 83.7 6.0 2.8 91.2 2.2 5200 6600 4400 3.6 0.070 181 93.8 5.7 1.4 92.9 4.0 9900 12200 7tO0 5.0 0.098 466 98.8 5.50.36 94.2 15.1 27000 ~5000 4.3 0.159 a) (MMA)3= conversion by NMR
b) No of Branches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer S c) by SEC vs. PMMA standards d) by SEC using universal calibration and viscometer e~ by SEC using light sc~LL~lillg detector Pol~...e. ~..lion of Butyl Acrylate with Vinylidene Methyl Methacrylate-10 Trimer as a Chain Transfer Agent and Macromonomer at 70~C.
Tr~T~rlient Amol-nt Toluene 8 g Decane 1 g (MMA)3= 7.5 g II Toluene 25 g 2,2'-azobis(2-methylbutanenitrile) 3 g III Butyl acrylate 32 g o The procedure described in EXAMPLE I was ~ollowed, three times higher 20 than in EXP. 1 initiator concentration was used. Data are shown in Table 2.
Table 2 Time CTA~ Pol~er C~ oSiLion No of Polymer (min) conv. (mole%) Br. Pe~ ~d~
(%) (MMA)3 MMA= BA Mol b) M ~) M c) M d) pDd) M " (dL/g) r 31.056.023.5 20.5 2.4 410 1200 ~0 36.649.59.9 40.5 5.0 2300 2100 46.824.513.0 62.5 1.9 1500 1800 62.814.58.0 77.6 1.8 2100 2600 1~0 88.112.02.7 85.3 4.5 5700 4200 123 96.76.6 1.0 92.4 6.7 14400 11500 143 99.15.20.36 94.4 14.5 25100 173 99.64.80.21 95.0 22.9 30200 360 99.84.90.16 94.9 30.6 29400 a) (MMA)3- conversion by NMR
b) No of Branches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer 5 c) by SEC vs. PMMA standards d) by SEC using u~ .sal calibration and viscometer e~ by SEC using light sc;~ detector Pol~ c. ~ali~.. of Butyl Acrylate with Vinylidene Methyl Methaclyiate-10 Trimer as a Chain Transfer Agent and Macromonomer at 80~C.
n~ riient Amonnt Toluene 8 g Decane 1 g (MMAh= 7.5 g II Toluene 25 g 2,2'-azobis(2-methylbutanenitrile) 1 g III Butyl acrylate 32 g The procedure described in EXAMPLE I was followed at 80~C. Kinetic 20 data are shown in Table 3.
Table 3 Time CTA~ PolymerC~ os.li~.. No of Polymer ~min) conv. (moie %) Br. Per Tld) (%) (MMA)3 MMA= BA Mol b) M ~) Mnc3 Mnd) PDd) Mn~) (dL/g) 2013.348.226.0 25.8 1.9 980 1600 ~, 4014.370.316.6 13.1 4.3 1700 1600 6024.645.5 9.9 44.6 4.6 2300 1600 8043.111.5 7.4 81.2 1.6 2200 2400 2100 1.3 0.~28 100 83.9 6.7 3.5 89.8 1.9 4100 4100 3400 1.4 0.043 120 93.7 5.8 1.6 92.6 3.6 9000 9800 5500 1.9 0.058 140 98.2 5.7 0.74 93.5 7.7 1o900 15000 5100 3.3 0.067 180 99.0 5.7 0.46 93.9 12.3 16600 5600 4.1 0.087 430 99.7 5.6 0.17 94.2 33.2 16100 6100 3.9 0.090 a) (MMA~3- conversion by NMR
b) No of Branches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer 5 c) by SEC vs. PMMA standards d) by SEC using ullIvt;-aial calibration and viscometer e~ by SEC using light sc~ nn~ detector POI~ ~ation of Butyl Acrylate with Vinylidene Methyl Methacrylate-10 Trimer as a Chain Tral.~r~r Agent and Macromonomer at 90~C.
~t Ir~redient .Amonnt Toluene 8 g Decane 1 g (MMA)3= 7.5 g II Toluene 25 g 2,2'-azobis(2-methylbutanenitrile) 1 g III Butyl acrylate 32 g ~j The procedure described in EXAMPLE 1 was followed at 90 ~C. Kinetic 20 data are shown in Table 4.
CA 022464l6 l998-07-3l WO 97/31031 PCTrUS97/02913 Table 4 Time CTA" Po~ymer Composition No of Polymer (min) conv. (mole %) Br. Per ~d) (%) (~IMA)3 MMAs BA Mol b) M ~) Mn~) Mnd) PD~ MnC) (dL/g) 10.336.333.8 30.0 1.1 740 1100 30.712.025.7 62.4 0.5 750 l900 60.312.213.6 74.2 0.9 1300 2000 88.210.65.9 83.5 1.8 2700 3600 100 99.07.40.87 91.7 8.5 16400 16700 3,400 2.4 0.040 120 100 5.10.14 94.8 36.3 355()0 9800 4.0 11000 0.132 145 100 3.20.12 96-7 26.3 25700 355U0 4.0 22000 0.221 340 100 3.00.10 96.9 29.9 338000 a) (MMA)3= conversion by NMR
b) No of Brar ches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer 5 C) by SEC vs. PMMA standards d) by SEC using u~ "sal calibration and viscometer e) by SEC using light sc~ g detf~ctor 10 Polr~..e~ ~alion of Butyl Acrylate with Vinylidene Methyl Methacrylate-Trimer as a Chain Transfer Agent and Macro~o~o,.~er at 100~C.
Ir~r~-li~nt Amollnt Toluene 8 g Decane 1 g ~MMA)3= 7.5 g II Toluene 25 g 2,2'-azobis(2-methylbnt~nenitrile) I g III Butyl acrylate 32 g The procedure described in EXAMPLE 1 was followed at 1 00~C. Kinetic data are shown in Table 5.
Table 5 Time CTA- Polymer Composition No of Polymer (min) conv. (mole %) Br. Per l~d) (%)(MMA)3 MMA= BA Mol.b) Mn ) MnC) Mnd~ PDd) MnC (dL/g) 20 21.7 16.4 28.1 55.6 0.6 730 1200 40 57.4 15.1 14.0 70.9 0.9 1200 1500 60 85.7 11.0 7.2 81.8 1.5 2200 2600 80 97.5 9.6 2.1 88.3 4.5 6900 4100 100 99.5 7.2 0.46 92.3 15.7 31000 13200 10500 4.3 0.078 120 99.8 5.5 0.20 94.3 27.6 15400 16300 3.7 0.125 142 99.6 S.0 0.15 94.9 33.0 15500 15400 3.7 0.118 175 99.0 5.0 0.16 94.9 31.0 13700 12300 4.2 0.114 310 99.4 5.0 0.11 94.9 45.0 20400 a) (MMA)3= conversion by NMR
S b) No of Branches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer c) by SEC vs. PMMA standards d) by SEC using universal calibration and viscometer e) by SEC using light sc~ g detector Table 6. Effect of Temperature and the Ratio of Butyl AcrylatetVinylidene Methyl Methacrylate Trimer on Nurnber of Branches Per Macromolecule.
EXAMPLE Temp (MMA)3= Number of Branch~s Mn (~C) (mole%)Per Molecule IH 13c~H NMR 13C NMR ~H NMR 13C NMR SEC.
NMR NMREG ) QC ) Control 8015.014.7 2.2 2.2 - 2,8002,400 ~,300 6 80 9.6 9.6 6.6 5.75.0 11,500 10,000 9,100 Control 8018.317.5 1.9 1.81.8 2,5002,400 3,200 7 80 9.1 8.8 7.7 6.77.2 13,700 12,200 10,700 8 1008.7 8.1 11.5 6.4 9.820,600 12,200 8,200 9 60 9.7 8.9 5.9 5.55.~ 10,300 9,800 11,900 60 7.110.1 6.1 - - 10,800 - 9,200 a) by SEC n THF, Mn vs. PMMA x 128/100 IM(BA)/M(MMA)]
5 b) EG - from end group analysis, the ratio of ~1/3 of the total methyl ester carbons minus (the average ofthe 2 vinyl carbons and the lln.~ r~te~l carbonyl carbon from the b-scission end group)] to [the average of the 2 vinyl carbons and the u ls~ dled C~IJOI1Y; carbon from the b-scission end group]
c) QC - from ~ ~ y carbon analysis, the ratio of ~the integral of the 10 ~lu~ carbon of the branch] to ~the average of the 2 vinyl carbons and the ul~dluldLed carbonyl carbon from the b-scission end group3 Table 7. Effect of Telllpc.d~L~re and the Ratio of Butyl Acrylate/Vinylidene Methyl Methacrylate Trimer on Number of Branches Per Macromolecule.
E~ (MMA)3= Number of Bran~hes Mn (temp.) (mole%) Pe~ Molecule ~H NMR 13CIH NMR13c NMR ~H NMR13c NMR SEC~
NMR
I l (80~C) 7.5 7.4 17 - 33,600 - 20,200 Control (80~C)14.814.4 3.7 3.5 4,900 4,800 3700 12 (80~C) 8.2 7.6 23 - 41,700 - 28,200 13 (100~C) 7.3 7.2 27 - - - 21,60~
14 (60~C) 8.2 7.1 13 - 25,000 - 27,600 15 (60~C) 7.5 7.9 56 - 107,~00 - 64,100 a) from universal calibration s nemon~tration of Rr~nche-l Stn~ re of Poly(butvl acrylates~ Prep~red U.cin~
Meth~yl M~th~rrylate Vir~ylidene Trimer (MMO3= as Ch~in Tr~n~t~er ~ent ~nll M~-~ro~non~ mer Linear poly(butyl acrylates) have an "a" coefficient of 0.70 in the Mark-Houwink equation, ~] = K Ma. Copolymers 3 in contrast have an "a" Mark-Houwink coefficient of 0.35-0.50, as would be expected for a polymer having a branched rather than a linear structure.
BRANCHED POLYMER SYNTHESIS
Precise macromolecular engineering using commodity monomers is S becoming a major trend in polymer technology to satisfy the clem~n-i for newproperties, improved cost effeetiveness, ecology and quality. Functional polymers with low molecular weight, low polydispersity, compact, branched struetures and t~rmin~lly loeated reaetive groups are expeeted to exhibit superior p~.rc,~ ee/eost eharaeteristies, by virtue of lower inherent viseosity and higher reactivity vs. eonventional linear statistieal eopolymers.
The t~rmin~lly funetional branehed polymers appear to be ultimate reactive substrates for networks, because the braneh points can substitute for asignificant portion of expensive reaetive groups and provide a ~etter eontroll of the reaetive groups distribution. Partieularly polymers having large numbers of short br~nehec below eritieal moleeular weight are unlikely to form any ~nt~ngl~ nent~ and should exhibit low inherent viseosity and good flow even in eoncellL~dLed solutions.
Conventional teehniques for sythe~i7in~ well defined branehed polymers require expensive mul*~t~p proeesses involving isolation of reaetive int~rmPtli~l.laclolllonomers. The macromonomers have polymerizable end groups, which are usually introdueed using funetional initiator, termin~ting or ehain transferagent. Well defined branehed polymers are prepared by the macromonomer homopolymerization or copolymerization with suitable low moleeular weight eomonomer seleeted based on known reaetivity ratios.
U.S. 4,680,352 describes molecular weight reduction and maeromonomer (polymers or copolymers with unsaturated end-groups) synthesis in copolymen7~tions with acrylates and styrene with various Co(II) complexes.
J. Antonelli, et. al., U. S. 5,362, 813 and C. Berge, et al., U. S. 5,362,826 diselose the p~ ~dLion of maeromonomers by radical addition-fr~men~tion processes and the copolymerization of maeromonomers. Branehed structures were not well charaeterized and the reincorporation of the branched macromonomers into more complex structures was not considered.
Dendrimers or h~ ui~lched polymers prepared using e.Ypensive. special multifunctional monomers or expensive multistep methods re~uiring repetitive isolation of the reactive interrne~ st-f c have been reviewed by J.C.Salamone, ed., Polymeric ~atf'rt~l~ Encyclopedia, Vol.5 (1996).
The references cited above cover the copolymeri_ation of vinyl monomers in the presence of chain transfer reagents, but do not disclose synthetic conditions for production of macromonomers or polymers cont~;ning branches upon branches.
SUMMARY OF TRrF TNVh,NTION
This invention relates to a general process for the synthesis of arlrlit;on polymers contz-ining branches upon hr~nrhf s and having a polymerizable olefin end group by a convenient one-pot polymerization of selected vinyl monomers with chain polymeri_ation initiators and a method to provide olefin end groups by chain transfer or tt~rrnin .tion agents. The pol~.n~,l;~lion is carried out in such a manner that chain transfer occurs frequently and each chain transfer event tf - ~JI;IIi~ that particular polymer chain with termin~l polymerizable olefinicfunctionality. Subsequent reincorporation of the polymer chains produced early in the reaction leads to br ~nrhing of subsequently-fo~med polymer chains which aretf ~ minate~l with polym~ i7~hle olefinic functionality. Subsequent reincorporation of the branched polymer chains leads to subsequently-forrned polymer chains cont~inin~ branches-upon-branches which are t-f nnin~t~d with polymerizable olefinic functionality. Spontaneous repetition of the process leads to highly branrh~cl or hyperbranched products still retaining termini with polymerizable olefinic functionality.
This invention concems an improved process for the free-radical polymerization of at least one unsaturated vinylic monomer to form a polymer whose molecular architecture includes branches upon branches and a polymerizable vinyl-terrnin~te(l end group, comprising contacting, in the ~scn~eof a free-radical initiator:
(i) one or more vinylic monomers having the formula CH2=CYZ and (ii) a chain transfer agent of formula CH2=CQ-CH2-X, wherein:
Y is selected from the group consisting of OR, O2CR, halogen, CO~H, COR, CO~R, CN, CONH2, CONHR. CONR, and R';
Z is selected H, CH3, or CH2OH;
R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted andunsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or dirr~ L and selected from the group consisting ofcarboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, ~ILilll~Ll,y amino, secon-i~ry amino, tertiary arnino, isocyanato, sulfonic acid and halogen, and the number of carbons in said alkyl groups is from 1 to 12; and R' is selected from the aromatic group con~i~ting of substituted and l-n~bstituted aryl, s~ and un~ul,~.liLu~ed heteroaryl, the snhstihlçnt~ being the same or different and selected from the group con~i~ting of carboxylic acid,carboxy}ic ester, epoxy, hydroxyl, alkoxy, ~lihll~y amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, s~bstitllt~d and unsubstituted alkyl,sllbstit-lt.od and L~ ub~liLuL~d aryl, ~ub~LiluLed and ull~ub~LiLuLed olefin andhalogen;
X is selected from -(CUY-CH23n-Z', S(O)R, S(O)2R, SnR3, halogen, R2 and R3;
U is selected from H and R;
Q is selected from Y, or in the case where X is halogen, Y and H;
Z' is selected from H, SRI, S(O~R, S(O)2R, R2 and R3;
nis2 1;
R is selected from the group substituted and unsubstituted alkyl, aryl.
aralkyl, alkaryl and org~nc)~ilicon groups wherein the snkstitllent(s~ are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
Rlis selected from the group H, substituted and unsubstituted alkyl. aryl, aralkyl, alkaryl and org~nr ~ilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl. alkoxy, amino and halogen;
R2 is selected from the group free radical initiator-derived fr~gment.~ of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, S alkoxyalkyl, alkoxyaryl, sulfate groups wherein the sub.lil~ (s) are independently selected from R, ORI, 07CR, halogen, CO2H and salts thereof, CO2R, CN, CONH2, CO2NHR, CONR2;
R3 is st?lected from the group free radical initiator-derived fr~gme~t~ of iL.,~A and lln.cllhst;tll~Pd alkyl, cycloalkyl, aryl, aralkyl, alkarvl, organosilyl, alkoxyalkyl, alkoxyary}, and P(O)R2 groups wherein the substituent(s) are independently selected from R, ORI, 02CR, halogen, CO2H and salts thereof, CO2R, CN, CON~2, CO2NHR, CONR2;
wherein the improvement comprises obtaining higher yields of polymer having the branch-upon-branch ~uellile-;LIlre and polymerizable vinylic chain termini, and a higher density of br~nch~os upon br~nl~h~ in that polymer by optimi7in~ the polymen7~t;0n in the following way: select step III and at least one of I; II; I and IV; and II and IV from steps:
I - decleasillg reactivity ratios of (i) and the resulting vinylic-term;n~t~d macromonomers and polymers toward O;
II - selecting the ratio of (i?/(ii) between 2 and 100, dependent on the values of 1, III and IV;
III - hlclea~ g the conversion of (i) and (;i) from 80% toward 100 %;
IV - i~ ea~hlg the temperature from 50~ toward 150~C.
Based on the disclosure and Examples presented herein, one skilled in the art will be readily able to select the optimum ratio of (i)/(ii) for any given class of monomer(s) and values of (i), (iii) and (iv) with minimum experimentation. One skilled in the art v~rill also be able to select the a~ l;ate chain transfer agent for the monomer(s~ being polym~ri7~ by reference to the well-known reactivity ratios of said chain transfier agents and monomer(s).
This invention further concerns the product of the above reaction which is composed primarily of a polymer having a branch-upon-branch structure and a polymerizable olefinic end group, having the structure:
X--CH2--C~H2--~ C~--f ~_C
\ /n \ /m \ Ip where B' =
X--CH2--C~H2--C~ Cl~z ~n \ /m \ /P
B" = X, B', H, CH3, CH2CHR'CH3, or CH2CMeR2CH3, n= 1-20,m=0-5,p=0-20;n+m+p>2;
and if m >1, then the m insertions are not consecutive. X, Y, Z, Rl and R2 are as earlier ~l~fine~l l)li',T~TT,Ti',T) DF~CRTPTION
We have discovered a general process for the synthesis of addition polymers co~ ;..i..g branches upon branches and having apolymerizable vinylic end group by a convenient one-pot polymeri_ation of selected vinyl monomers with chain polymerization initiators and a method to provide olefin end groups by 20 chain transfer or t~ ion agents. The polymeri7~tion is carried out in such a manner that chain transfer occurs frequently and that each chain transfer event terminates that particular polymer chain termin~tecl with polymerizable olefinicfunctionality. The process is shown in Scheme 1.
Scheme 1.
5 Step t. rO-, ~n of llncar ~.,a~",.onaa._.s 1 r~ tiO., UNsA~ EDuMc~NoMER Chain Transfer or Tt~ n P~ liu-~/
UM ChainTransfer Step ~r.,- ~ nofprimary~ ed.. a~,.ull.unu.. _.a 2 orTe~.~l k 1 Stcp3. F~- ~- hof branch-upon-branch .. ~c~o.. ~u.,l~mers 3 Pol~ L~ ùn/
UM ChalnTransfer or Tennination etc Sul~se~lu~.ll r~,hlcc..~oldlion of the polymer chains produced early in the reaction 25 leads to l,.~...fh;..~ of subsequently-forrned polymer chains which are terrnin~tt?d with poly~ .,~l,le olefinic fi-n~tion~1ity. Subsequent reincorporation of the br~n~ ~d polymer chains leads to ~l,se-luently-formed palymer chains cont~inin branches-upon-l,.dllches which are t~rrnin~ted with polymerizab}e olefinic fi~nctionality. Spontaneous repetition of the process leads to highly branched or 30 hyp~blallched products still ret~ininp~ terrnini with polymerizable olefinic functionality.
The polymers made by the present process are useful in a wide variety of co~tings Other potential uses can include cast, blown, spun or sprayed applications in fiber, film, sheet, composite materials, multilayer co~t;ng~, photopolymeri_able materials, photoresists, surface act;ve agents, dispersants.
5 adhesives, adhesion promoters, coupling agents, commpatibilizers and others.
End products taking advantage of available characteristics can include, for example, automotive and arçhit~-ctl~ral coatings or fini~hç~, including high solids, aqueous or solvent based fini.~hes Polymers, such as those produced in this invention, would find use in, for example, structured polymers for use in pigment 1 0 dis~
In a l),cr~.ied process the free-radical initiator is selected from azo initiators, typical examples of which include: 2,2'-a_obis(isobutyronitrile), VAZO-88 = l,1'-~obis(cyclohex~ne-l-c~l,ollik;le) (DuPont Co., Wilmington, DE) VR-110 = 2,2'-azobis(2,4,4-trimt;Lllyl~el-la..e) (Wako Pure Chemir~l Industries, Ltd., Osaka, Japan) Chain transfer reagents, CH2=CQ-CH2-X, can be based upon vinylidene macromonomers ~c~ed by several methods. A good example is the methyl methacrylate trimer, CH2=C(CO2Me)-CH2-CMe(CO2Me)-C~2-CMe(CO2Me)-CH3. These radical addition-fr~gment~tion chain transfer agents have been 2~ reviewed by E. Ri zardo, et al., Macromol. Symp. 98, 101 (1995).
Other organic chain transfer reagents include allylic sulfides, sulfones, bromides, phosphonates, sf~nnRnes, vinylidene termin~fe~1 methacrylic oligomers,a-methyl styrene dimer and related compounds. Preferred chain transfer agents and polym~ i7~hle interme~i~te macromonomers exhibit dual reactivity, in that 25 they can both undergo copolymerization or homopolymerization as well as promote colllpclilive chain transfer through the addition-elimination process.
Substituent Q of the chain transfer reagent is chosen to convey the a~lo~liate reactivity of the olefinic group in radical polymerization of the desired monomer~s) under polymerization conditions. The substituents Q and X can also 30 be chosen so as to introduce any required end-group functionality into the polymer. Therefore using functional chain transfer agent (iii) can be a preferedmethod. These end groups can be the same or different and can be chosen such that the final polymer can be telechelic. Suitable end groups are particularly those compatible with free radical polymerization and include epoxy, hydroxyl, S carboxyl, silyl.
The process can be potentially con~ te~ by bulk, solution, suspension or emulsion polymerization using batch or preferably starved feed reactor, which offers better process control.
The treelike branched polymers are formed by in situ generation and 10 copolym~-i7~tion of first linear and subsequently increasingly branched macromonomers through the polymerizable olefin group. The method was demonstrated by model kinetic studies of monomer, chain transfer agent (CTA) conversions, polymer molecular weight increase combined with qll~ntit~tive end group and br~n..hing characteri_ation when reacting vinylidene MMA-kimer used 15 as a CTA and butyl acrylate ~BA) in a starved-feed reactor. Macromolecules typically with 2 to 30 branches each c~ 5 to 20 monomers were prepared, branch length being primarily controlled by the monomer/chain transfer agent ratio, conversion and to some extend by t~ lpc;ldlul~.
A chain polymeri7~tion is conkolled by a chain transfer step so as to 20 provide a polymeri7~hle olefin end group (Scheme 1~. The branch-upon-branch ~l~u~ e is buik by in situ generation and copolylllc,i~Lion of linear and subsequently increasingly branched macromonomers through the polymerizable olefin group.
That monomer copolymeri7~hility is primarily determined by the steric 25 and eleckonic properties is well doc1-mentecl in the art. The chain process can involve either one or several different comonomers. Typical monomers include acrylates, methacrylates, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, a-methylstyrene, halogenated olefins, vinyl esters, butalso can include N-vinyl carbazole, N-vinyl pyrrolidone,and dienes such as 30 isoprene, and chloroprene.
Quantitative NMR analysis of the products, particularly end group structure and br~nching, combined with oligomer analvsis by MALDI mass CA 022464l6 l998-07-3l ~.~e~ osco~ show that conventional radical termination and chain transfer processes can be effectively suppressed under these conditions, when acrylates (or styrene) are copolymerized with the vinylidene macromonomer/chain transfer agent . The polymer molecular weight and end group structure are predominantly controlled by the ~-scission chain transfer. High conversions (usually 80-90 %) of the vinylidene end group are predominantly achieved by the incorporation, i.e., copolymeri7~tion leading to branches. The data are consistent with a mech~ni~m, in which the initially forrned branched macromolecules receive predominantly thevinylidene end group through the ~-scission chain transfer. Having a reactive vinylidene end group allows the singly-branched macromolecules to participate inanalogous subsequent (secondary) copolymerization steps leading eventually to even more branched structures, which could be called branch-upon-branch polymers.
Formation of branch-upon-branch ~ul;Lul~s is indicated by the signifir~nt } 5 ir~ ,ase in the polymer molecular weight and in the number of branches per polymer molecule that occurs even at nearly complete conversion of the vinylidene (MMA)3=, which was used as a chain transfer agent and model macromonomer and at high acrylate monomer conversions. The development of ~'h~r~ ion methods for branched polymer formation from vinylidene macromonomers by NMR, SEC, GC, MALDI mass spectroscopy was ecst-nti~l for developing and CO~ 1 ion of this method of mal~ing branch-upon-branch structures, see E. McCord, et al., ACS Polymer Prep. 36 (2), 106 (1995).
Br~nçhing density ~stim~tecl from the ratio of grafting to ,~-scission is primarily clet~TTnin~(i by the BA/chain transfer agent ratio, conversion and to some extend by te~ )eld~ in the range 60 to 100 ~C. Under standard conditions, one MMA-trimer branch occurs per 8 to 16 BA comonomers con~llme-l, which corresponds to l 000 - 2,000 molecular weight of BA segment per one ~ranch and is desirably below an entanglement length.
The copolymers were characterized by lH and 13C NMR, by conventional SEC using RI detector vs. PMMA standards and compared with data obtained using universal calibration in THF and the light-scattering weight-average molecular weights. Under typical radical copolYmerization conditions in starved CA 02246416 l99X-07-31 feed reactor used in these studies, about a I 0-fold molar excess of acrylate comonomer over mPth~rrylate vinylidene macromonomer is required to achieve acceptable yield (> 10 %) and a significant number (>5) of branches per macromolecule. The number of 5 branches per molecule is a min;murn (per 5 definition) for branch-upon-branch structures.
Kinetic data at early and int~rme~ t~ conversions showed as expected that ~-scission is favored over incorporation by higher L~ aLulcs. At almost complete vinylidene group collvcL~iion, the effect of tcLllpcidluLe on the overall ratio of incorporation to ~-scission was found to be small. This is evidently due to 10 somewhat higher activation energy of the competing ~-scission vs. the incol~olaLion and due to the fact that incorporation is a major merh~ni~m of thevinylidene group con~ Lion.
Pl~r~ cd monomers are:
methyl acrylate, 15 ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers3, 2-ethylhexyl acrylate, isobornyl acrylate, 20 acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, glycidyl acrylate, 25 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), diethylaminoethyl acrylate, triethyleneglycol acrylate.
30 N-tert-butyl acrylamide, N-n-butyi acrylamide, N-methyl-ol acrylamide, CA 022464l6 l998-07-3l N-ethyl-ol acrylamide, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, 5 Aimçthoxymethylsilylpropyl acrylate, diethoxymethylsilylpLoyyl acrylate, dibutoxymethylsilylpropyl acrylate, diisoyuoyo~ymet-h-ylsilylpropyl acrylate, ~iim~thoxysilylyruyyl acrylate, 10 diethoxysilylyl()yyl acrylate, dibutoxysilylylo~yl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, vinyl propionate, 15 vinyl butyrate, vinyl bt?n7.0ate, vinyl chloride, vinyl fluoride, vinyl bromide.
20 methyl methacrylate, ethyl meth~r.rylate, propyl meth~rrylate (all isomers), butyl m~th~rrylate (all isomers), 2-ethylhexyl methacrylate, 2~ isobornyl meth~r.rylate, methacrylic acid, benzyl methacrylate, - phenyl melllacl ylate, methacrylonitrile, 30 alpha methyl styrene, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethyl-silylpropylm~,acl ylate, dibutoxymethylsilylpropyl methacrylate, 5 diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibuLu2~y~ilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, isoE~lo~ yl ~)UIyld~
isolJIo~u~llyl acetate, iS~ Io~ yl b~n7n~tf iSO~O,,u~llyl chlor~
iso~Lopcllyl fluoride, 15 i~o~lo~ yl bromide itaconic acid itaconic anhydride d~ llyl itC~n:~t~, methyl itaconate 20 N-tert-butyl m~th~r.rylamide, N-n-butyl methacrylamide, N-methyl-ol methacrylamide, N-ethyl-ol methacrylamide, iso~ .,ylbenzoic acid (all isomers), 25 diethylamino ~lrh~nlethylstyrene (all isomers), para-methyl-alpha-methylstyrene (all isomers), diisopropenylbenzene (all isomers), isoL~ enylbenzene sulfonic acid (all isomers), methyl 2-hydroxymethylacrylate, 30 ethyl 2-hydroxymethylacrylate, propyl 2-hydroxymethylacrylate (all isomers), butyl 2-hydroxymethylacrylate (all isomers), 2-ethylhexyl 2-hydroxymethylacrylate.
isobornyl 2-hydroxymethylacrylate, styrene, vinyl benzoic acid (all isomers), S diethylamino styrene (all isomers), para-methylstyrene (all isomers), divinylbenzene ~all isomers), and vinyl benzene sulfonic acid (all isomers).
~X~1~1PT,F.C~
F,~r~ples 1-15:
P~ lion of Br~nch-Upon-Rr~nch Poly(butyl acrylates) U~in,p Meth~yl Meth~ylate Vin~ lene Trimer (MM~.)3_ 15~ Ch~in Tr~n~fer A~ent ~n~l Macromonorner This procedure illustrates the plepa alion, analysis and proof of the branch-upon-branch polymer archit~c~lre in which there are at least 5 branches in a starved feed reactor by a multi step/one pot process. Conditions of the branch-20 upon-branch ~llu;Lu~e formation are identified from the effects of L~m~ dl~e,monomer, chain transfer agent and initiator concentrations and conversion on thepolymer structure. The broken line in each of the following Tables will indicatewhere significant levels of branch-upon-branch polymers are produced.
The polymers of this invention with the most desirable plu~ Lies are those 25 having at least 10%, more preferably at least 25%, and most preferably above 50%, branch upon branch architecture.
WO 97131031 rCT/US97/02913 EXAI~IPLE I
Polymerization of Butyl Acrylate w~th Vinylidene l~Iethyt Methacrylate-Trimer as a Chain Transfer Agent and Macromonomer at 70~C.
5 Part r~r~ nt Amol-nt Toluene 8 g Decane 1 g (MM~)3=
II Toluene 25 g 2,2'-a7obis(2-methylbl-t~nP.nitrile) 1 g III Butyl acry}ate 32 g Part I was charged into the reactor equipped with stirrer, reflux condenser, thermocouple, and nitrogen positive ~ ule, and heated to 70~C. Part II and III
were fed con.,ul.c,,,lly into the reactor over 150 and 120 minllte~, respectively.
After completing the addition of Part II, the reactor collL~llL~ were held at 80~C for an additional 60 minllte~ The copolymeri7~tion kinetics have been followed by gas chromatography, NMR and GPC. ~5 g samples of the reaction mixture were withdrawn at 20 min. intervals followed by GC ~ltotennin~tion of the BA and 20 vinylidene MMA-trimer conc~l.LldLions. Volatiles were stripped on high vacuumfor several hours and the oligomers/polymers were analyzed by NMR and GPC.
Decane was used as an internal standard and molar response factors were d~t-ormin-ocl using ~ Lul~s of known composition cont~ining SCT MMA-trimer, BA and decane. The kinetic data are shown in Table 1. Polymer composition was 25 followed by Matrix Assisted Laser Desorption lonization (MALDl) Mass Spectroscopy. Polymer molecular weight was measured by S~C and viscometry.
Structure of both polymers, including br~nching density and end groups, was characterized by lH and ~3C NMR.
Table I
Time CTA' Polymer Composition No of Polymer (min) conv. (mole%) Br. Per ~d) (%)(MMA)3 MMA= E~A Mn Mn Mnd) PDd) Mne) (dL/g) 23 24.839.318.7 42.0 ~.1 1200 1100 43 25.139.318.0 42.8 2.2 1300 1600 63 36.419.911.4 68.7 1.7 1600 2100 83 48.410.7 7.8 81.5 1.4 2100 2600 103 63.4 8.2 6.1 ~5.7 1.4 2500 3100 2400 2.4 0.055 120 75.5 7.3 3.8 88.9 1.9 3900 4300 3800 3.2 0.~61 140 83.7 6.0 2.8 91.2 2.2 5200 6600 4400 3.6 0.070 181 93.8 5.7 1.4 92.9 4.0 9900 12200 7tO0 5.0 0.098 466 98.8 5.50.36 94.2 15.1 27000 ~5000 4.3 0.159 a) (MMA)3= conversion by NMR
b) No of Branches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer S c) by SEC vs. PMMA standards d) by SEC using universal calibration and viscometer e~ by SEC using light sc~LL~lillg detector Pol~...e. ~..lion of Butyl Acrylate with Vinylidene Methyl Methacrylate-10 Trimer as a Chain Transfer Agent and Macromonomer at 70~C.
Tr~T~rlient Amol-nt Toluene 8 g Decane 1 g (MMA)3= 7.5 g II Toluene 25 g 2,2'-azobis(2-methylbutanenitrile) 3 g III Butyl acrylate 32 g o The procedure described in EXAMPLE I was ~ollowed, three times higher 20 than in EXP. 1 initiator concentration was used. Data are shown in Table 2.
Table 2 Time CTA~ Pol~er C~ oSiLion No of Polymer (min) conv. (mole%) Br. Pe~ ~d~
(%) (MMA)3 MMA= BA Mol b) M ~) M c) M d) pDd) M " (dL/g) r 31.056.023.5 20.5 2.4 410 1200 ~0 36.649.59.9 40.5 5.0 2300 2100 46.824.513.0 62.5 1.9 1500 1800 62.814.58.0 77.6 1.8 2100 2600 1~0 88.112.02.7 85.3 4.5 5700 4200 123 96.76.6 1.0 92.4 6.7 14400 11500 143 99.15.20.36 94.4 14.5 25100 173 99.64.80.21 95.0 22.9 30200 360 99.84.90.16 94.9 30.6 29400 a) (MMA)3- conversion by NMR
b) No of Branches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer 5 c) by SEC vs. PMMA standards d) by SEC using u~ .sal calibration and viscometer e~ by SEC using light sc;~ detector Pol~ c. ~ali~.. of Butyl Acrylate with Vinylidene Methyl Methaclyiate-10 Trimer as a Chain Transfer Agent and Macromonomer at 80~C.
n~ riient Amonnt Toluene 8 g Decane 1 g (MMAh= 7.5 g II Toluene 25 g 2,2'-azobis(2-methylbutanenitrile) 1 g III Butyl acrylate 32 g The procedure described in EXAMPLE I was followed at 80~C. Kinetic 20 data are shown in Table 3.
Table 3 Time CTA~ PolymerC~ os.li~.. No of Polymer ~min) conv. (moie %) Br. Per Tld) (%) (MMA)3 MMA= BA Mol b) M ~) Mnc3 Mnd) PDd) Mn~) (dL/g) 2013.348.226.0 25.8 1.9 980 1600 ~, 4014.370.316.6 13.1 4.3 1700 1600 6024.645.5 9.9 44.6 4.6 2300 1600 8043.111.5 7.4 81.2 1.6 2200 2400 2100 1.3 0.~28 100 83.9 6.7 3.5 89.8 1.9 4100 4100 3400 1.4 0.043 120 93.7 5.8 1.6 92.6 3.6 9000 9800 5500 1.9 0.058 140 98.2 5.7 0.74 93.5 7.7 1o900 15000 5100 3.3 0.067 180 99.0 5.7 0.46 93.9 12.3 16600 5600 4.1 0.087 430 99.7 5.6 0.17 94.2 33.2 16100 6100 3.9 0.090 a) (MMA~3- conversion by NMR
b) No of Branches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer 5 c) by SEC vs. PMMA standards d) by SEC using ullIvt;-aial calibration and viscometer e~ by SEC using light sc~ nn~ detector POI~ ~ation of Butyl Acrylate with Vinylidene Methyl Methacrylate-10 Trimer as a Chain Tral.~r~r Agent and Macromonomer at 90~C.
~t Ir~redient .Amonnt Toluene 8 g Decane 1 g (MMA)3= 7.5 g II Toluene 25 g 2,2'-azobis(2-methylbutanenitrile) 1 g III Butyl acrylate 32 g ~j The procedure described in EXAMPLE 1 was followed at 90 ~C. Kinetic 20 data are shown in Table 4.
CA 022464l6 l998-07-3l WO 97/31031 PCTrUS97/02913 Table 4 Time CTA" Po~ymer Composition No of Polymer (min) conv. (mole %) Br. Per ~d) (%) (~IMA)3 MMAs BA Mol b) M ~) Mn~) Mnd) PD~ MnC) (dL/g) 10.336.333.8 30.0 1.1 740 1100 30.712.025.7 62.4 0.5 750 l900 60.312.213.6 74.2 0.9 1300 2000 88.210.65.9 83.5 1.8 2700 3600 100 99.07.40.87 91.7 8.5 16400 16700 3,400 2.4 0.040 120 100 5.10.14 94.8 36.3 355()0 9800 4.0 11000 0.132 145 100 3.20.12 96-7 26.3 25700 355U0 4.0 22000 0.221 340 100 3.00.10 96.9 29.9 338000 a) (MMA)3= conversion by NMR
b) No of Brar ches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer 5 C) by SEC vs. PMMA standards d) by SEC using u~ "sal calibration and viscometer e) by SEC using light sc~ g detf~ctor 10 Polr~..e~ ~alion of Butyl Acrylate with Vinylidene Methyl Methacrylate-Trimer as a Chain Transfer Agent and Macro~o~o,.~er at 100~C.
Ir~r~-li~nt Amollnt Toluene 8 g Decane 1 g ~MMA)3= 7.5 g II Toluene 25 g 2,2'-azobis(2-methylbnt~nenitrile) I g III Butyl acrylate 32 g The procedure described in EXAMPLE 1 was followed at 1 00~C. Kinetic data are shown in Table 5.
Table 5 Time CTA- Polymer Composition No of Polymer (min) conv. (mole %) Br. Per l~d) (%)(MMA)3 MMA= BA Mol.b) Mn ) MnC) Mnd~ PDd) MnC (dL/g) 20 21.7 16.4 28.1 55.6 0.6 730 1200 40 57.4 15.1 14.0 70.9 0.9 1200 1500 60 85.7 11.0 7.2 81.8 1.5 2200 2600 80 97.5 9.6 2.1 88.3 4.5 6900 4100 100 99.5 7.2 0.46 92.3 15.7 31000 13200 10500 4.3 0.078 120 99.8 5.5 0.20 94.3 27.6 15400 16300 3.7 0.125 142 99.6 S.0 0.15 94.9 33.0 15500 15400 3.7 0.118 175 99.0 5.0 0.16 94.9 31.0 13700 12300 4.2 0.114 310 99.4 5.0 0.11 94.9 45.0 20400 a) (MMA)3= conversion by NMR
S b) No of Branches Per Molecule = (MMA)3in polymer/MMA= vinylidene ends in polymer c) by SEC vs. PMMA standards d) by SEC using universal calibration and viscometer e) by SEC using light sc~ g detector Table 6. Effect of Temperature and the Ratio of Butyl AcrylatetVinylidene Methyl Methacrylate Trimer on Nurnber of Branches Per Macromolecule.
EXAMPLE Temp (MMA)3= Number of Branch~s Mn (~C) (mole%)Per Molecule IH 13c~H NMR 13C NMR ~H NMR 13C NMR SEC.
NMR NMREG ) QC ) Control 8015.014.7 2.2 2.2 - 2,8002,400 ~,300 6 80 9.6 9.6 6.6 5.75.0 11,500 10,000 9,100 Control 8018.317.5 1.9 1.81.8 2,5002,400 3,200 7 80 9.1 8.8 7.7 6.77.2 13,700 12,200 10,700 8 1008.7 8.1 11.5 6.4 9.820,600 12,200 8,200 9 60 9.7 8.9 5.9 5.55.~ 10,300 9,800 11,900 60 7.110.1 6.1 - - 10,800 - 9,200 a) by SEC n THF, Mn vs. PMMA x 128/100 IM(BA)/M(MMA)]
5 b) EG - from end group analysis, the ratio of ~1/3 of the total methyl ester carbons minus (the average ofthe 2 vinyl carbons and the lln.~ r~te~l carbonyl carbon from the b-scission end group)] to [the average of the 2 vinyl carbons and the u ls~ dled C~IJOI1Y; carbon from the b-scission end group]
c) QC - from ~ ~ y carbon analysis, the ratio of ~the integral of the 10 ~lu~ carbon of the branch] to ~the average of the 2 vinyl carbons and the ul~dluldLed carbonyl carbon from the b-scission end group3 Table 7. Effect of Telllpc.d~L~re and the Ratio of Butyl Acrylate/Vinylidene Methyl Methacrylate Trimer on Number of Branches Per Macromolecule.
E~ (MMA)3= Number of Bran~hes Mn (temp.) (mole%) Pe~ Molecule ~H NMR 13CIH NMR13c NMR ~H NMR13c NMR SEC~
NMR
I l (80~C) 7.5 7.4 17 - 33,600 - 20,200 Control (80~C)14.814.4 3.7 3.5 4,900 4,800 3700 12 (80~C) 8.2 7.6 23 - 41,700 - 28,200 13 (100~C) 7.3 7.2 27 - - - 21,60~
14 (60~C) 8.2 7.1 13 - 25,000 - 27,600 15 (60~C) 7.5 7.9 56 - 107,~00 - 64,100 a) from universal calibration s nemon~tration of Rr~nche-l Stn~ re of Poly(butvl acrylates~ Prep~red U.cin~
Meth~yl M~th~rrylate Vir~ylidene Trimer (MMO3= as Ch~in Tr~n~t~er ~ent ~nll M~-~ro~non~ mer Linear poly(butyl acrylates) have an "a" coefficient of 0.70 in the Mark-Houwink equation, ~] = K Ma. Copolymers 3 in contrast have an "a" Mark-Houwink coefficient of 0.35-0.50, as would be expected for a polymer having a branched rather than a linear structure.
Claims (8)
1. An improved process for the free-radical polymerization of at least one unsaturated vinylic monomer to form a polymer whose molecular architecture includes branches upon branches and a polymerizable vinyl-terminated end group, comprising contacting (i) one or more vinylic monomers having the formula CH2=CYZ, and (ii) a chain transfer agent of formula CH2=CQ-CH2-X, wherein:
Y is selected from the group consisting of OR, O2CR, halogen, CO2H, COR, CO2R, CN, CONH2, CONHR, CONR2 and R';
Z is selected H, CH3, or CH2OH;
R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted andunsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid and halogen, and the number of carbons in said alkyl groups is from 1 to 12; and R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid,carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato. sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen;
X is selected from -(CUY-CH2)n-Z', S(O)R, S(O)2R. SnR3, halogen, R2 and R3;
U is selected from H and R;
Q is selected from Y. or in the case where X is halogen, Y and H;
Z' is selected from H, SR1, S(O)R, S(O)2R, R2 and R3:
n is ~ 1;
R is selected from the group substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
R'is selected from the group H, substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
R2 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, sulfate groups wherein the substituent(s) are independently selected from R, OR1, O2CR, halogen, CO2H and salts thereof, CO2R, CN, CONH2, CO2NHR, CONR2;
R3 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, and P(O)R2 groups wherein the substituent(s) are independently selected from R, OR1, O2CR, halogen, CO2H and salts thereof, CO2R, CN, CONH2, CO2NHR, CONR2;
wherein the improvement comprises obtaining higher yields of polymer having the branch-upon-branch architecture and polymerizable vinylic chain termini, and a higher density of branches upon branches in that polymer by optimizing the polymerization in the following way: select step III and at leastone of I; II; I and IV; and II and IV from steps:
I - decreasing reactivity ratios of (i) and the resulting vinylic-terminated macromonomers and polymers toward 0;
II - selecting the ratio of (i)/(ii) between 2 and 100, dependent on the values of I, III and IV;
III - increasing the conversion of (i) and (ii) from 80% toward 100 %;
IV - increasing the temperature from 50° toward 150°C.
Y is selected from the group consisting of OR, O2CR, halogen, CO2H, COR, CO2R, CN, CONH2, CONHR, CONR2 and R';
Z is selected H, CH3, or CH2OH;
R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted andunsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid and halogen, and the number of carbons in said alkyl groups is from 1 to 12; and R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid,carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato. sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen;
X is selected from -(CUY-CH2)n-Z', S(O)R, S(O)2R. SnR3, halogen, R2 and R3;
U is selected from H and R;
Q is selected from Y. or in the case where X is halogen, Y and H;
Z' is selected from H, SR1, S(O)R, S(O)2R, R2 and R3:
n is ~ 1;
R is selected from the group substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
R'is selected from the group H, substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
R2 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, sulfate groups wherein the substituent(s) are independently selected from R, OR1, O2CR, halogen, CO2H and salts thereof, CO2R, CN, CONH2, CO2NHR, CONR2;
R3 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, and P(O)R2 groups wherein the substituent(s) are independently selected from R, OR1, O2CR, halogen, CO2H and salts thereof, CO2R, CN, CONH2, CO2NHR, CONR2;
wherein the improvement comprises obtaining higher yields of polymer having the branch-upon-branch architecture and polymerizable vinylic chain termini, and a higher density of branches upon branches in that polymer by optimizing the polymerization in the following way: select step III and at leastone of I; II; I and IV; and II and IV from steps:
I - decreasing reactivity ratios of (i) and the resulting vinylic-terminated macromonomers and polymers toward 0;
II - selecting the ratio of (i)/(ii) between 2 and 100, dependent on the values of I, III and IV;
III - increasing the conversion of (i) and (ii) from 80% toward 100 %;
IV - increasing the temperature from 50° toward 150°C.
2. A process according to Claim 1 wherein Z = H.
3. A process according to Claim 1 wherein X = (CUY-CH2)n-Z',
4. A process according to Claim 1 wherein, in (i), Z=H and. in (ii), X= (CUY-CH2)n-Z'.
5. A process according to Claim 1 wherein Z' is substituted alkyl, aryl, aralkyl, alkaryl, organosilyl wherein the reactive substituents(s) are independently selected from the group carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, amino and halogen.
6. A process according to Claim 3 wherein:
Z is H;
Q is CO2R; and the molar ratio if (i)/(ii) is 5 to 30; and conversion of each of (i) and (ii) is 85 to 100%.
Z is H;
Q is CO2R; and the molar ratio if (i)/(ii) is 5 to 30; and conversion of each of (i) and (ii) is 85 to 100%.
7. A composition of matter comprising a polymer having a branch-upon-branch structure and a polymerizable olefinic end group, having the structure:
where B' =
B" = X, B', H, CH3, CH2CHR1CH3, or CH2CMeR2CH3, X is selected from -(CUY-CH2)n-Z', S(O)R, S(O)2R, SnR3, halogen, R2 and R3;
Y is selected from the group concicting of OR, O2CR, halogen, CO2H, COR, CO2R, CN, CONH2, CONHR, CONR2 and R';
Z is selected H, CH3, or CH2OH;
R1 is selected from the group H, substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
R2 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, sulfate groups wherein the substituent(s) are independently selected from R, OR1, O2CR, halogen, CO2H and salts thereof, CO2R, CN, CONH2, CO2NHR, CONR2;
n= 1-20, m=0-5, p=0-20; n+m+p~2;
and if m >1, then the m insertions are not consecutive.
where B' =
B" = X, B', H, CH3, CH2CHR1CH3, or CH2CMeR2CH3, X is selected from -(CUY-CH2)n-Z', S(O)R, S(O)2R, SnR3, halogen, R2 and R3;
Y is selected from the group concicting of OR, O2CR, halogen, CO2H, COR, CO2R, CN, CONH2, CONHR, CONR2 and R';
Z is selected H, CH3, or CH2OH;
R1 is selected from the group H, substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
R2 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, sulfate groups wherein the substituent(s) are independently selected from R, OR1, O2CR, halogen, CO2H and salts thereof, CO2R, CN, CONH2, CO2NHR, CONR2;
n= 1-20, m=0-5, p=0-20; n+m+p~2;
and if m >1, then the m insertions are not consecutive.
8. A composition according to Claim 7 wherein X is (CUY-CH2)n-Z',
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| US6316519B1 (en) * | 1997-02-19 | 2001-11-13 | E. I. Du Pont De Nemours And Company | Molecular weight controlled polymers by photopolymerization |
| AU752670B2 (en) | 1997-04-23 | 2002-09-26 | Commonwealth Scientific And Industrial Research Organisation | Method of macromonomer synthesis |
| US6740723B2 (en) * | 1997-07-17 | 2004-05-25 | E. I. Du Pont De Nemours And Company | Branched polyolefin synthesis |
| 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 |
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| DE19959927A1 (en) | 1999-12-11 | 2002-02-07 | Basf Coatings Ag | Aqueous primary dispersions and coating materials, processes for their preparation and their use |
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| US6384172B1 (en) | 2001-01-02 | 2002-05-07 | Michigan Molecular Institute | Hyperbranched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof |
| US6534600B2 (en) * | 2001-03-26 | 2003-03-18 | Michigan Molecular Institute | Hyperbranched polyureas, polyurethanes, polyamidoamines, polyamides and polyesters |
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| WO2003076479A1 (en) * | 2002-03-08 | 2003-09-18 | Basell Poliolefine Italia S.P.A. | Process for the polymerization of olefins |
| US20070066777A1 (en) * | 2004-09-03 | 2007-03-22 | Bzowej Eugene I | Methods for producing crosslinkable oligomers |
| DE602007010256D1 (en) * | 2006-03-28 | 2010-12-16 | Council Scient Ind Res | WATER-SOLUBLE MACROMONOMERS WITH UNSATURATED CLOSURE AND METHOD FOR PRODUCING THEM |
| US7579420B2 (en) | 2006-04-04 | 2009-08-25 | E. I. Du Pont De Nemours And Company | Hyperbranched maleic anhydride-diene polymers |
| US7579403B2 (en) * | 2006-04-04 | 2009-08-25 | E. I. Du Pont De Nemours And Company | Stain resist comprising hyperbranched maleic anhydride-diene polymers |
| JP5284265B2 (en) * | 2006-10-04 | 2013-09-11 | ザ ユニバーシティ オブ アクロン | Synthesis of inimer and hyperbranched polymers |
| US8748548B2 (en) * | 2009-12-28 | 2014-06-10 | Johnson & Johnson Vision Care, Inc. | Macromonomer mixture, terminal-reactive polymer mixture, intermediate for macromonomer and silicone hydrogel |
| EP2436713A1 (en) * | 2010-09-29 | 2012-04-04 | Sika Technology AG | Two-Part Polyurethanes based on Hyperbranched Polymers |
| CN103261244B (en) * | 2010-12-22 | 2016-01-06 | 巴塞尔聚烯烃股份有限公司 | Method by making ethene, difunctionality or multifunctional comonomer and other optional comonomer prepare ethylene copolymer under radical polymerization initiator exists |
| WO2012165473A1 (en) | 2011-05-30 | 2012-12-06 | 三菱レイヨン株式会社 | Polymer and method for producing same |
| CN103483477B (en) * | 2013-09-18 | 2015-10-14 | 西北工业大学 | The preparation method of single dispersing surface chain transfer activity functionalized polymer microsphere |
| JP6500982B2 (en) | 2016-05-19 | 2019-04-17 | 三菱ケミカル株式会社 | Macromonomer copolymer and method for producing the same |
| EP3321331B1 (en) * | 2016-11-10 | 2020-10-21 | Agfa-Gevaert | Solder mask inkjet inks for manufacturing printed circuit boards |
| KR102366957B1 (en) | 2017-09-06 | 2022-05-11 | 미쯔비시 케미컬 주식회사 | Macromonomer copolymer, epoxy resin composition, adhesive, molding material and cured product |
| JP7243988B2 (en) | 2017-11-24 | 2023-03-22 | 三菱ケミカル株式会社 | Block copolymer composition and method for producing the same |
| JPWO2022149524A1 (en) | 2021-01-08 | 2022-07-14 |
Family Cites Families (14)
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| JPS4834882B1 (en) * | 1969-04-21 | 1973-10-24 | ||
| JPS4834882A (en) * | 1971-09-13 | 1973-05-22 | ||
| US4680352A (en) * | 1985-03-01 | 1987-07-14 | E. I. Du Pont De Nemours And Company | Cobalt (II) chelates as chain transfer agents in free radical polymerizations |
| US5324879A (en) * | 1985-12-03 | 1994-06-28 | Commonwealth Scientific And Industrial Research Organisation | Oligomerization process |
| US4680354A (en) * | 1986-05-21 | 1987-07-14 | The Glidden Company | Low molecular weight polymers and copolymers |
| US5264530A (en) * | 1992-05-01 | 1993-11-23 | E. I. Du Pont De Nemours And Company | Process of polymerization in an aqueous system |
| 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. |
| US5773534A (en) * | 1992-05-22 | 1998-06-30 | E. I. Du Pont De Nemours And Company | Preparing crosslinkable polymers employing macromonomer chain transfer agents |
| US5310807A (en) * | 1992-12-30 | 1994-05-10 | E. I. Du Pont De Nemours And Company | Star polymers made from macromonomers made by cobalt chain transfer process |
| US5770665A (en) * | 1993-12-20 | 1998-06-23 | Zeneca Limited | Free radical polymerization process |
| DK0788518T3 (en) * | 1994-10-28 | 1999-12-27 | Zeneca Ltd | Free radical polymerization process |
| AUPM930494A0 (en) * | 1994-11-09 | 1994-12-01 | Commonwealth Scientific And Industrial Research Organisation | Polymerization in aqueous media |
| US5587431A (en) * | 1995-04-21 | 1996-12-24 | E. I. Du Pont De Nemours And Company | Synthesis of terminally unsaturated oligomers |
| ES2207717T3 (en) * | 1996-02-23 | 2004-06-01 | E.I. Du Pont De Nemours And Company | SYNTHESIS OF RAMIFIED POLYMERS. |
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