WO2022117389A1 - Method for producing a terminal-functional polymer - Google Patents

Method for producing a terminal-functional polymer Download PDF

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Publication number
WO2022117389A1
WO2022117389A1 PCT/EP2021/082551 EP2021082551W WO2022117389A1 WO 2022117389 A1 WO2022117389 A1 WO 2022117389A1 EP 2021082551 W EP2021082551 W EP 2021082551W WO 2022117389 A1 WO2022117389 A1 WO 2022117389A1
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Prior art keywords
acrylate
acid
methacrylate
ether
tert
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PCT/EP2021/082551
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French (fr)
Inventor
Zhen Yuan QU
Jing Luo
Timo Mangel
Xiao Hui Li
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Basf Se
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Publication of WO2022117389A1 publication Critical patent/WO2022117389A1/en

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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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the present invention relates to a method for producing a terminal-functional polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization, a polymer obtained by this method and the use of said polymer for sealant or adhesive application, and a method for RAFT end group removal.
  • RAFT reversible addition-fragmentation chain transfer
  • hybrid systems are getting more and more attention recently. Such systems combine the properties of functional groups and soft polymer backbone to afford a number of advantages, e.g. high backbone flexibility and high elongation, excellent elongation recovery, good adhesion to various substates, low shrinkage, non-staining and paintable, and low VOC.
  • Functional polymers made by conventional free radical polymerization are known to suffer from poor mechanical property, as the functional groups are randomly distributed along the polymer backbone, leading to an ill-defined polymer network with many short polymer segments between neighboring crosslinking points.
  • Polymers with functional group only on polymer terminals or close to terminals are known to enhance mechanical property of the materials after curing.
  • the advent of controlled radical polymerization technology has allowed the synthesis of polymers where the functional groups are only placed on polymer terminals or close to polymer terminals.
  • Reversible addition-fragmentation chain transfer (RAFT) polymerization is a well- established technology for making polymers with such tailored architecture.
  • US 2004220364A1 discloses a process of making telechelic silyl-terminated polyacrylates by using RAFT polymerization, with the following steps: (a) RAFT polymerization of acrylates, (b) converting RAFT end group into thiol group by aminolysis, and (c) end group functionalization by reacting terminal thiol group with isocyanate silane.
  • the process disclosed in US 2004220364A1 involves one more step for polymer end group functionalization and has less than one silane group in each polymer terminal.
  • the objective of the invention is to provide a simple synthetic route towards terminal-functional polymers, particularly silyl-terminated polymers, using RAFT polymerization.
  • Another objective of the invention is to provide a cheap and simple method for RAFT end group removal for silyl-terminated polymers.
  • Still another objective is to show the curability and advantageous mechanical properties of the resulting polymer, compared with random copolymer. Such properties are useful for sealant or adhesive applications.
  • the present invention relates to a method for producing a terminal-functional polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of at least one thiocarbonylthio group-containing compound, comprising the steps of
  • the present invention relates to a terminal-functional polymer, especially a silyl-terminated polymer obtained by the method according to the present invention.
  • the present invention relates to a sealant or adhesive composition, comprising the polymer according to the present invention.
  • the present invention relates to the use of the polymer according to the present invention for sealant or adhesive application.
  • the present invention relates to the removal of RAFT end group for silyl- terminated polymers, by aminolysis in the presence of silyl compounds.
  • the polymerization can be done in one-pot with no purification step needed in-between, and the number of terminal functional groups can be tuned to afford a required need for curing speed and density.
  • the method according to the present invention is simple and cheap and easy to scale up.
  • the terminal-functional polymer obtained by the method according to the present invention provides significantly improved elongation properties for sealant or adhesive applications.
  • Figure 1 shows sample's initial length and length before broken by a manual stretching method.
  • One aspect of the present invention relates to a method for producing a terminal-functional polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of at least one thiocarbonylthio group-containing compound, comprising the steps of
  • the vinyl monomer used in the present invention is not particularly limited as long as it is radically polymerizable.
  • vinyl monomers which may be used include methacrylate esters, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2- hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dime
  • any form may be acceptable, such as a random copolymer, a block copolymer, a graft copolymer, or a combination of any of these.
  • vinyl monomers described above preferred are styrene, a-methylstyrene, vinyl chloride, vinylidene chloride, methacrylate esters, acrylate esters, methacrylonitrile, acrylonitrile, vinyl acetate, and maleimide compounds, more preferred are methacrylate esters and acrylate esters, and most preferred are methyl methacrylate, n-butyl acrylate, or a combination of these.
  • the thiocarbonylthio group-containing compound used in the present invention is at least one compound selected from the group consisting of a compound represented by general formula (I): wherein
  • R is selected from the group consisting of alkyl, substituted alkyl, aralkyl, substituted aralkyl, a polyvalent aliphatic hydrocarbon group, a polyvalent aromatic hydrocarbon group, a polyvalent araliphatic hydrocarbon group, a polyvalent alipharomatic hydrocarbon group, a polyvalent aliphatic hydrocarbon group containing a heteroatom, and a polyvalent aromatic hydrocarbon group containing a heteroatom; preferably from the group consisting of phenyl, benzyl, 1- phenylethyl, 2-(2-phenyl)propyl, 1 -acetoxyethyl, 1-(4-methoxyphenyl)ethyl, ethoxycarbonylmethyl, 2-(2-ethoxycarbonyl)propyl, 2-(2-cyano)propyl, tert-butyl, 1 , 1 ,3,3- tetramethylbutyl, 2-[2-(p-chlorophenyl)]prop
  • Z is selected from the group consisting of alkyl, substituted alkyl, alkoxy, aryloxy, aryl, substituted aryl, aralkyl, substituted aralkyl, N-aryl-N-alkylamino, N,N-diarylamino, N,N- dialkylamino, thioalkyl, and dialkylphosphinyl; and preferably from the group consisting of C 2 - Ci6-alkyl, -S-C 2 -Ci6-alkyl, -O-C 2 -Ci 6 -alkyl, phenyl, benzyl, 4-chlorophenyl, 1-naphthyl, 2-naphthyl, diethoxyphosphinyl, thiomethyl (methylsulfide), phenoxy, thiophenyl, N,N-dimethylamino, N,N- diethylamino, N-phenyl-N-methyl
  • the thiocarbonylthio group-containing compounds used in the present invention may be used alone or in combination.
  • the thiocarbonylthio group-containing compound When the vinyl monomer used in the present invention is polymerized, the thiocarbonylthio group-containing compound must be present in the reaction system during polymerization.
  • the addition method for the thiocarbonylthio group-containing compound is not particularly limited.
  • the thiocarbonylthio group-containing compound is dissolved or dispersed in the reaction system before polymerization is initiated.
  • the thiocarbonylthio group-containing compound is preferably dissolved in a solvent or a vinyl monomer before addition.
  • the amount of the thiocarbonylthio group-containing compound used is not particularly limited. Since the degree of polymerization of the resultant polymer depends on the number of moles of the thiocarbonylthio group-containing compound added, the amount of the thiocarbonylthio group-containing compound may be calculated based on the required degree of polymerization or number-average molecular weight of the polymer.
  • the monomer carrying functional groups comprises at least one monomer having the formula (II): wherein R 1 is H or methyl and R 2 represents or contains a crosslinkable functional group.
  • the crosslinkable functional group is not particularly restricted, but may include one or more of crosslinkable silyl, carboxyl, epoxy, hydroxyl and acrylamide groups, provided that when the vinyl monomer contains hydroxyl, the crosslinkable functional group is not hydroxyl.
  • the monomer carrying silyl groups is at least one compound selected from the group consisting of a compound represented by general formula (11-1): wherein R 3 is H or methyl, Z 1 is Ci-C 4 -alkylene, preferably propylene, each X is independently of one another -OCH 3 , -OCH 2 CH 3 or -OCH 2 CH 2 CH 3 , and Y is H, -CH 3 , -OCH 3 , -OCH 2 CH 3 or - OCH 2 CH 2 CH 3 .
  • general formula (11-1) wherein R 3 is H or methyl, Z 1 is Ci-C 4 -alkylene, preferably propylene, each X is independently of one another -OCH 3 , -OCH 2 CH 3 or -OCH 2 CH 2 CH 3 , and Y is H, -CH 3 , -OCH 3 , -OCH 2 CH 3 or - OCH 2 CH 2 CH 3 .
  • the monomer carrying silyl groups includes y- methacryloxypropyltrimethoxysilane, Y-methacryloxypropyltriethoxysilane, y- methacryloxypropyltripropoxysilane, y-methacryloxypropylmethyldimethoxysilane, y- methacryloxypropylmethyldiethoxysilane, y-methacryloxypropylmethyldipropoxysilane, methacryloxymethyldimethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, (methacryloxymethyl)-methyldimethoxysilane,
  • the monomer carrying carboxyl groups includes, for example, unsaturated carboxylic acids containing from 3 to about 20 carbon atoms.
  • the unsaturated carboxylic acids include, among others, acrylic acid, methacrylic acid, itaconic acid, beta carboxy ethyl acrylate, mono-2- acroyloxypropyl succinate, and the like.
  • the monomer carrying epoxy groups includes, for example, glycidyl methacrylate and glycidal acrylate.
  • a particularly preferred epoxy functional monomer is commercially available under the designation S-100 from Synasia. That monomer is 3,4 epoxycydohexylmethyl methacrylate, [CAS 82428-30-6], having a chemical formula CHHI 6 O 3 and a molecular weight of 196.2.
  • the monomer carrying acrylamide groups includes, for example, (meth)acrylamide and its derivatives including the N-substituted alkyl and aryl derivatives thereof. These include N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide and the like.
  • the monomer carrying hydroxyl groups includes, for example, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyethylcaprolactone(meth)acrylate and the like.
  • the polymerization initiator or polymerization initiation method used is not particularly limited, and any polymerization initiator or polymerization initiation method commonly used in the art may be employed.
  • polymerization initiators include, but are not limited to, peroxide polymerization initiators, such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1 ,1 ,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butyl-a-cumyl peroxide, di-a-cumyl peroxide, 1 ,4- bis[(tert-butylperoxy)isopropyl]benzene, 1 ,
  • polymerization initiators may be used alone or in combination. It may also be possible to use a polymerization initiation system by electron irradiation, X-ray irradiation, radiation irradiation, or the like. With respect to polymerization initiation methods, the methods described in Moad and Solomon "The Chemistry of Free Radical Polymerization", Pergamon, London, 1995, pp. 53-95 may be employed.
  • the amount of polymerization initiator used is not particularly limited.
  • the amount of radical species generated during polymerization is preferably 1 mole or less, and more preferably 0.5 moles or less, relative to 1 mole of thiocarbonylthio group in the thiocarbonylthio group- containing compound.
  • temperature is controlled in the case of the polymerization initiator which causes thermal dissociation, or the amount of energy is controlled in the case of the polymerization initiation system which generates radicals by light or electron beams.
  • the polymerization reaction is carried out preferably at temperatures which allow the polymerization initiator to have a half-life of 0.5 to 50 hours, more preferably at temperatures which allow the polymerization initiator to have a half-life of 1 to 20 hours, and most preferably at temperatures which allow the polymerization initiator to have a half-life of 5 to 15 hours.
  • the polymerization can be carried out in the presence of polymerization media.
  • the polymerization media can be solvents.
  • solvents which may be used include, but are not limited to, hydrocarbon solvents, such as heptane, hexane, octane, and mineral spirit; ester solvents, such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, and diethylene glycol monobutyl ether acetate; ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; alcohol solvents, such as methanol, ethanol, isopropanol, n-butanol, secbutanol, and isobutanol; ether solvents, such as tetrahydrofuran, diethyl ether, dibutyl ether, dioxane, ethylene glycol di
  • solvents may be used alone or in combination.
  • the types and amounts of solvent used may be determined in consideration of the solubility of the monomers, the solubility of the resultant polymer, the polymerization initiator concentration and the monomer concentration suitable for achieving a satisfactory reaction rate, the solubility of the thiocarbonylthio group-containing compound, effects on human body and environment, availability, cost, etc., and are not particularly limited.
  • the polymerization media can be plasticizers.
  • the plasticizer as used in accordance with the invention may comprise one or more selected from the group consisting of: phthalates, trimellitates, aliphatic dibasic esters, polyesters, polymeric, epoxides, phosphates.
  • said plasticizer is selected from the group consisting of : butyl benzyl phthalate, butyl 2-ethylhexyl phthalate, diisohexyl phthalate, diiso-heptyl phthalate, di(2- ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, disononyl phthalate, diisodecyl phthalate, diiso undecyl phthalate, diisotredecyl phthalate, diiso (Cu, Ci 2 , C ) phthalate, di(n- butyl) phthalate, di(n-C 7 , C 9 ) phthalate, di(n-C 6 , C 8 , Cw) phthalate, diiso(n-nonyl) phthalate, di(n- C 7 , C 9 , Cu) phthalate, di(n-C
  • said plasticizer is selected from the group consisting of: diisohexyl phthalate, diisoheptyl phthalate, di(2-ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, disononyl phthalate, diisodecyl phthalate, diiso undecyl phthalate, diisotredecyl phthalate, diiso (Cu, Ci 2 , Cw) phthalate, di(n-butyl) phthalate, di(n-C 7 , C 9 ) phthalate, di(n-C 6 , C 8 , Cw) phthalate, diiso(n-nonyl) phthalate, di(n-C 7 , C 9 , Cu) phthalate, di(n-C 9 , Cu) phthalate, di(n-undecyl) phthalate, tri(n-C 8
  • polymerization can be carried out in batch, semi-batch, and continuous processes, preferably in semi-batch processes.
  • polymerization temperature is about 60 to 90 °C, preferably about 65 to 80 °C.
  • the total polymerization time is 3 to 15 h, preferably 4 to 10 h.
  • the method for producing a terminal-functional polymer further comprises step (c) removing the RAFT end groups by aminolysis.
  • the thiocarbonylthio group-containing vinyl polymer is allowed to react with amine compounds.
  • the amine compounds include amines and their analogues.
  • the amine compounds of the present invention also include amides and nitrogen-containing aromatic compounds which are analogous to amines.
  • examples of such amine compounds include, but are not limited to, hydroxylamine sulfate, hydroxylamine, N-(2-aminoethyl)ethanolamine, N-methylethanolamine, 12-aminododecanoic acid, 3-amino-1 -propanol, amine-modified acrylic polymers, allylamine, diallylamine, isopropylamine, diisopropylamine, 3,3'-iminobis(propylamine), ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, 3-(2-ethylhexyloxy)propylamine, 3- ethoxypropylamine, diisobutylamine, 3-(diethylamino)propylamine, di-2-e
  • ammonia When ammonia is used, as in primary or secondary amines with a boiling point of 100 °C or less, excess ammonia can be removed by distillation under reduced pressure, and thereby the purification step can be simplified, which is preferable.
  • the amount of amine compounds used is not particularly limited and preferably 0.5 to 1 ,000 moles, preferably 1 to 200 moles, more preferably 1 to 20 moles, and most preferably 1 to 10 moles, based on 1 mole of thiocarbonylthio group.
  • the reaction conditions are not particularly limited.
  • a method in which the polymer is dissolved in an organic solvent, and the amine compound is added thereto; a method in which the amine compound is added to a water-based dispersion or emulsion; or a method in which the amine compound is directly added to the solid or molten polymer itself may be employed.
  • the treatment temperature is not particularly limited.
  • the treatment temperature is -50 °C to 300 °C, preferably - 10 °C to 200 °C, more preferably 10 °C to 100 °C, and most preferably 30 °C to 90 °C.
  • the method for producing a silyl-terminated polymer further comprises step (c1) removing the RAFT end groups by aminolysis in the presence of a silane group-containing compound represented by general formula (III):
  • R 4 — Si — X 1 x1 (HD wherein R 4 is C 8 -Ci 6 -alkyl, vinyl group, or C 2 -Ci 0 -alkyl substituted or interupted by one or more amine groups, and each X 1 is independently of one another -OCH 3 , -OCH 2 CH 3 or - OCH 2 CH 2 CH 3 .
  • R 4 is C 2 -C -alkyl, prerferably C 3 -C 8 -alkyl, more prerferably C 3 -C 6 - alkyl, substituted or interupted by one or more amine groups, prerferably one, two or three amine groups, more prerferably one or two amine groups.
  • silane group-containing compounds include vinyltrimethoxysilane, (3- aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2- aminoethyl)-N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, prerferably vinyltrimethoxysilane, (3-aminopropyl)trimethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.
  • Another aspect of the present invention relates to a terminal-functional polymer, especially a silyl-terminated polymer obtained by the method according to the present invention.
  • the molecular weight of the resultant polymer is not particularly limited and is set depending on the application.
  • the number-average molecular weight (M n ) determined by gel permeation chromatography (GPC) is in the range of 10,000 to 1 ,000,000, preferably in the range of 20,000 to 500,000, and more preferably in the range of 30,000 to 200,000.
  • the molecular weight distribution of the resultant polymer is not particularly limited.
  • the ratio (M w /M n ) of the weight-average molecular weight (M w ) to the number-average molecular weight (M n ) determined by gel permeation chromatography (GPC) is 3 or less, preferably 2 or less, and more preferably 1.5 or less.
  • the degree of polymerization for a radically polymerizable vinyl monomer is not particularly limited and is set depending on the number-average molecular weight (M n ).
  • the degree of polymerization for monomer carrying functional groups is in the range of 1 .0 to 5, preferably in the range of 1 .2 to 4.
  • Another aspect of the present invention relates to a sealant or adhesive composition, comprising the polymer according to the present invention.
  • the sealant or adhesive composition according to the present invention may contain catalysts as necessary.
  • the catalysts include, but are not limited to, titanate esters, such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds, such as dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; lead compounds, such as lead octylate; amine compounds, such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine
  • C 2 to C 6 carboxylic acid such as acetic acid, valeric acid; a poly-carboxylic acid such as citric acid, malic acid, maleic acid, succinic acid, malonic acid, hippuric acid, tartaric acid, oxalic acid; a medium/long chain acid such as lauric acid, stearic acid; phosphoric acids such as phenyl phosphoric acid; any other acid such as levulinic acid, benzoic acid, boric acid, trifluoroacetic acid; organic bismuth compound, such as bismuth carboxylate, especially bismuth octoate, bismuth ethylhexanoate, bismuth neodecanoate or bismuth pivalate.
  • These catalysts may be used alone or in combination.
  • the amount of catalyst used is not particularly limited.
  • the catalyst is used in an amount of 0 to 10% by weight relative to the polymer according to the present invention.
  • the sealant or adhesive composition according to the present invention may also include one or more additives, such as those described below.
  • the composition includes Ultraviolet (UV) light absorbers selected from the group consisting of hydroxyphenylbenzotriazole, tris-aryl-s-triazine, hydroxybenzoate, 2-hydroxybenzophenone and cyanoacrylate ultraviolet light absorbers (UVAs).
  • UV light absorbers selected from the group consisting of hydroxyphenylbenzotriazole, tris-aryl-s-triazine, hydroxybenzoate, 2-hydroxybenzophenone and cyanoacrylate ultraviolet light absorbers (UVAs).
  • the UVA may include 5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)- 2H-benzotriazole, 2-(3,5-bis-a-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 4,6-diphenyl-2-(4- hexyloxy-2-hydroxyphenyl)-s-triazine, 4,6-bis-(2,4-dimethy
  • UVAs are commercial, for example TINUVIN 326, TINUVIN 234, TINUVIN 1577, TINUVIN 1600, CYASORB UV 1164, CYASORB THT, CYASORB UV 2908, CHIMASSORB 81 , UVINUL 3030, ADK LA-F70, ADK LA-1000, TINUVIN 400, etc.
  • fillers based on magnesium silicate hydrate such as, for example, talc, based on aluminum hydroxide such as, for example, AI(OH) 3 , based on a feldspar, based on quartz powder and/or based on a calcium silicate and/or aluminum silicate may be used and may have a particle size from 1 to 20 micrometers. Adding one or more fillers may serve to improve the mechanical properties of the composition.
  • the fillers are chosen from calcium silicate, magnesium silicate hydrate, aluminum silicate, quartz powder and/or aluminum hydroxide such as, for example, aluminum trihydrate. Fillers based on CaCO 3 , TiO 2 , carbon black and/or BaSO 4 as well as fillers with a significant Fe content and/or containing additional heavy metals may be used.
  • Lightweight fillers in particular those based on polyurethane including their copolymers, polyamide wax and/or polyolefin wax may also be used. Lightweight fillers may also be used to reduce the density of the sealant or adhesive composition. Alternatively or additionally, hollow filing bodies may also be used.
  • Thixotropy agents in particular based on feldspar, silicic acid/silica, fumed silica, sepiolite and/or bentonite may be used to adjust rheological properties, in particular for thixotropic behavior, of the composition.
  • Plasticizers in particular based on an adipate, a benzoate, a citrate, a phthalate, a hydrogenated phthalate, an ester of a polyethylene glycol, and/or a terphenyl, preferably the same plasticizer used as polymerization media as decribed hereinabove, may be used, for example, to increase the flexibility of the sealant or adhesive composition.
  • Adhesion promoters may be used to improve the adhesion of the sealant or adhesive composition to a substrate.
  • suitable adhesion promoters for improving adhesion include silane containing compounds, such as organosilanes, aminosilanes, epoxysilanes, amino alkoxy silanes, vinyl alkoxy silanes, isocyanato alkoxy silanes, isocyanurate functional alkoxy silanes, (meth)acrylic silanes, anhydridosilanes or adducts of the aforementioned silanes with primary aminosilanes, aminosilanes or urea silanes, polyamines such as polyethyleneimine, or combinations thereof.
  • adhesion promoters can include vinyltriethoxysilane, vinyltrimethoxysilane, vinyl tris(2-methoxyethoxysilane), vinyl triisopropoxysilane, (meth)acryloyloxypropyl trimethoxy silane, y-(meth)acryloxypropyl trimethoxysilane, y-(meth)acryloxypropyl triethoxysilane, (3- methacryloxypropyl)-trimethoxysilane, (3-methacryloxypropyl)-triethoxy silane, (3- methacryloxypropyl)-triisopropoxy silane, 2-methyl-2-propenoic acid 3-[tris-(1-methylethoxy)- silyl]-propyl ester, (3-methacryloxypropyl)-methyldiethoxysilane, 3-glycidoxypropyl methyldiethoxy silane, 3-glycidoxypropylmethyldimethoxysilane,
  • the organosilane comprises vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2- methoxyethoxysilane), vinyl triisopropoxysilane, gamma-methacryloxypropyltrimethoxy silane, or combinations thereof.
  • the organosilane can comprise vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma- isocyanato propyl trimethoxysilane, n-beta-(aminoethyl) gamma-aminopropyl trimethoxy silane, n-(2-aminoethyl)-3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl dimethoxy silane, bis-(gamma-trimethoxysilylpropyl amine), n-phenyl-gamma-aminopropyltrimethoxysilane, gamma-isocyanato propyl methyl dimethoxy silane, beta-(3,4-epoxycyclohexyl) ethyl triethoxy silane,
  • the adhesion promoter can include poly amines (i.e., polymers formed from either an amine-group containing monomer or an imine monomer as polymerized units such as aminoalkyl vinyl ether or sulfides; acrylamide or acrylic esters, such as dimethyl- aminoethyl(meth)acrylate; N-(meth)acryloxyalkyl-oxazolidines such as poly(oxazolidinylethyl methacrylate), N-(meth)acryloxyalkyltetrahydro-l,3-oxazines, and monomers that readily generate amines by hydrolysis).
  • Suitable polyamines can include, for example, poly(oxazolidinylethyl methacrylate), poly(vinylamine), or polyalkyleneimine (e.g., polyethyleneimine).
  • the amount of the adhesion promoter present in the compositions can be 0% by weight or greater (e.g., 1% by weight or greater, 2% by weight or greater, 3% by weight or greater, 4% by weight or greater, 5% by weight or greater, 6% by weight or greater, 8% by weight or greater, 10% by weight or greater, 12% by weight or greater, or 15% by weight or greater), based on the total weight of the composition.
  • Anti-aging agents may also be used, such as sterically hindered phenols, phenyleneamine and/or hindered amine light stabilizers such as 4,6-bis(dodecylthiomethyl)-o-cresol, ethylene- bis(oxyethylene)bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), thiodiethylene-bis(3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionate), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)-propionate) and/or phenylene amines such as, for example, N-isopropyl-N'- phenyl-p-phenylenediamine.
  • hindered amine light stabilizers such as 4,6-bis(dodecylthiomethyl)-o-cresol, ethylene-
  • Anti-aging agents may be used to scavenge the free radicals formed due to aging processes involving the composition and may contribute to delaying and/or preventing aging such as yellowing or embrittlement of the sealant or adhesive composition.
  • Dehydrating agents e.g. those based on an organofunctional alkoxysilane, based on a zeolite such as an alkali aluminum zeolite and/or based on a mono functional isocyanate may also be used.
  • Flame retardants in particular those based on phosphate esters, based on ammonium polyphosphate, based on melamine, based on aluminum hydroxide and/or based on magnesium hydroxide may also be used to improve the fire prevention behavior of the sealant or adhesive composition such as, for example, to delay the onset of burning of the sealant or adhesive, to spontaneously terminate the burning process and/or to reduce the formation of smoke.
  • Vulcanization promoters may also be used, such as diphenylguanidine, thiuram, and/or sulfur (e.g. sulfur paste).
  • Whitening agent or colorant may also be used, such as TiO 2 , pigments and/or dyes.
  • At least one organic solvent in particular based on an ester and/or an ether such as, for example, ethyl acetate and/or monopropylene glycol monomethyl ether can be used.
  • Another aspect of the present invention relates to the use of the polymer according to the present invention for sealant or adhesive application.
  • Butyl acrylate (BA) is from Sigma. Plasticizers Hexamoll DINCH and Plastomoll DNA are BASF products.
  • RAFT agent is from Boron Molecular (BM1812).
  • CaCO 3 is from Si- nopharm.
  • Acid catalyst is from Islechem, LLC (M103).
  • precipitated calcium carbonate (PCC) is from Guangxi Huana New Material Technology Co., Ltd (CCS-25, 80 nm).
  • Ground calcium carbonate (GCC) is Omycarb 5 (5 pm).
  • Organotin catalyst dibutyltin diacety- lacetonate, DBTA
  • DBTA is from Nitto Kasei Co., Ltd (U-220H). All other reagents are from Sinopharm.
  • Theoretical number-average molecular weight (M n ) of a polymer synthesized can be estimated by the following eguation:
  • Mn 1 - r rn - ⁇ * C% + M ( RAFT ) wherein [Monomer] and [RAFT] are concentrations (mol/L) of monomer and RAFT agent, respectively. C% is the monomer conversion. M(mon) and M(RAFT) are molecular weights of monomer and RAFT agent, respectively.
  • Target number-average molecular weight (M n ) is the theoretical M n estimated by above eguation when assuming monomer conversion (C%) is 100%.
  • Molecular weight and polydispersity of polymers are determined by gel permeation chromatography (GPC) using PSS SDV 10e5/10e4/10e3 columns (300*8 nm) and THF as eluent. The polymers are dissolved in THF at 1.5 mg/mL for 12 h at room temperature, filtered by 0.45 pm membrane before injection. The molecular weight is calibrated by conventional GPC against polystyrene (PS) standards.
  • PS polystyrene
  • the telechelic polymer with a target number-average molecular weight (M n ) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the soft polymer backbone is poly (butyl acrylate), and the target DP of it is 390 in case of 100% monomer conversion, determined by the molar ratio of butyl acrylate to RAFT agent.
  • the functional silane groups are chain extended via 3-(trimethoxysilyl) propyl acrylate (TSPA), and the DP of each end group is 2, determined by the molar ratio of 3-(trimethoxysilyl)propyl acrylate to 2 times of RAFT agent (two polymer terminals in one chain). Therefore, the telechelic polymer has a target chemical formula: TSPA 2 BA 390 TSPA 2 .
  • the BA390 was synthesized in the first step. RAFT agent, butyl acrylate and Hexamoll DINCH in amounts shown in Table 1 were added in initial charge. With N 2 bubbling for 30 minutes, the resulting mixture was then heated to 68 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 was added for 150 minutes, feed 2 for 180 minutes, and the polymerization was kept for 210 minutes. The reaction was heated to 75 °C, then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 135 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 85%.
  • the monomer conversion of the first step is 95.0%. After chain extension with TSPA, the final monomer conversion overall is 98.6%.
  • the telechelic polymer with a target number-average molecular weight (M n ) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the soft polymer backbone is poly (butyl acrylate), and the DP of it is 390, determined by the molar ratio of butyl acrylate to RAFT agent.
  • the functional silane groups are chain extended via [3- (Methacryloyloxy)propyl]trimethoxysilane (MEMO), and the DP of each end group is 2, determined by the molar ratio of [3-(Methacryloyloxy)propyl]trimethoxysilane to 2 times of RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO2BA390MEMO2.
  • the BA390 was synthesized in the first step. RAFT agent, butyl acrylate and ethyl acetate in amounts shown in Table 2 were added in initial charge. With N 2 bubbling for 30 minutes, the resulting mixture was then heated to 68 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 was added for 150 minutes, feed 2 for 180 minutes, and the polymerization was kept for 210 minutes. The reaction was heated to 75 °C, then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 135 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 85%.
  • the conversion of the first step is 95.4%.
  • the final conversions of butyl acrylate and MEMO are 98.2% and 91.0%, respectively.
  • the telechelic polymer with a target number-average molecular weight (M n ) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the soft polymer backbone is poly (butyl acrylate), and the DP of it is 390, determined by the molar ratio of butyl acrylate to RAFT agent.
  • the functional silane groups are chain extended via 3- Methacryloxypropylmethyldimethoxysilane (MEDMO), and the DP of each end group is 2, determined by the molar ratio of 3-Methacryloxypropylmethyldimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEDMO2BA390MEDMO2.
  • the BA390 was synthesized in the first step. RAFT agent, butyl acrylate and ethyl acetate in amounts shown in Table 3 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 76 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 was added for 150 minutes, feed 2 for 180 minutes, and the polymerization was kept for 210 minutes. Then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 135 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 85%. Table 3: Semi-batch synthesis of MEDMO2BA390MEDMO2
  • the conversion of the first step is 95.2%.
  • the final conversions of butyl acrylate and MEDMO are 99.6% and 100%, respectively.
  • the telechelic polymer with a target number-average molecular weight (M n ) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the soft polymer backbone is poly (butyl acrylate), and the DP of it is 390, determined by the molar ratio of butyl acrylate to RAFT agent.
  • the functional silane groups are chain extended via [3-(Methacryloyloxy) pro- pyl]trimethoxysilane, and the DP of each end group is 4, determined by the molar ratio of [3- (Methacryloyloxy)propyl]trimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO4BA390MEMO4.
  • the BA390 was synthesized in the first step. RAFT agent, butyl acrylate and ethyl acetate in amounts shown in Table 4 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 68 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 was added for 150 minutes, feed 2 for 180 minutes, and the polymerization was kept for 210 minutes. The reaction was heated to 75 °C, then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 135 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 85%.
  • the conversion of the first step is 96.5%.
  • the final conversions of butyl acrylate and MEMO are 97.8% and 73.8%, respectively.
  • M n number-average molecular weight
  • the telechelic polymer with a target number-average molecular weight (M n ) of 100,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the soft polymer backbone is poly (butyl acrylate), and the DP of it is 780, determined by the molar ratio of butyl acrylate to RAFT agent.
  • the functional silane groups are chain extended via [3-(Methacryloyloxy) pro- pyl]trimethoxysilane, and the DP of each end group is 4, determined by the molar ratio of [3- (Methacryloyloxy)propyl]trimethoxysilane to 2 times of RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO4BA780MEMO4.
  • the BA 7 SO was synthesized in the first step. RAFT agent, butyl acrylate, Plastomoll DNA and AIBN in amounts shown in Table 5 were added in initial charge. With N 2 bubbling for 30 minutes, the resulting mixture was then heated to 70 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 was added for 60 minutes and the polymerization was kept for 240 minutes. Then feed 2 was added for 15 minutes and the polymerization was kept for 285 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 65%.
  • the conversion of first step is 91.4%.
  • the final conversions of butyl acrylate and MEMO are 98.1% and 100%, respectively.
  • the telechelic polymer with a target number-average molecular weight (M n ) of 70,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the soft polymer backbone is poly (butyl acrylate), and the DP of it is 546, determined by the molar ratio of butyl acrylate to RAFT agent.
  • the functional silane groups are chain extended via [3-(Methacryloyloxy) propyl] trimethoxysilane, and the DP of each end group is 4, determined by the molar ratio of [3- (Methacryloyloxy)propyl]trimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO4BA546MEMO4.
  • the BA546 was synthesized in the first step. RAFT agent, butyl acrylate, Plastomoll DNA and AIBN in amounts shown in Table 6 were added in initial charge. With N 2 bubbling for 30 minutes, the resulting mixture was then heated to 70 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 was added for 60 minutes and the polymerization was kept for 240 minutes. Then feed 2 was added for 15 minutes and the polymerization was kept for 285 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 70%.
  • the conversion of first step is 93.22%.
  • the final conversions of butyl acrylate and MEMO are 98.39% and 100%, respectively.
  • the telechelic polymer with a target number-average molecular weight (M n ) of 40,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the soft polymer backbone is poly (butyl acrylate), and the DP of it is 312, determined by the molar ratio of butyl acrylate to RAFT agent.
  • the functional silane groups are chain extended via [3-(Methacryloyloxy) propyl] trimethoxysilane, and the DP of each end group is 1.2, determined by the molar ratio of [3- (Methacryloyloxy) propyl]trimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO12BA312MEMO12.
  • the BA312 was synthesized in the first step. RAFT agent and Hexamoll DINCH in amounts shown in Table 7 were added in initial charge. With N 2 bubbling for 30 minutes, the resulting mixture was then heated to 76 °C under N2 atmosphere. Under stirring, feed 1 was added for 90 minutes, feed 2 for 120 minutes, and the polymerization was kept for 210 minutes. Then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 75 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 90%.
  • the conversion of first step is 96.7%.
  • the final conversions of butyl acrylate and MEMO are 98.6% and 100%, respectively.
  • M n number-average molecular weight
  • the telechelic polymer with a target number-average molecular weight (M n ) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the functional silane groups are chain extended via [3-(Methacryloyloxy) propyl] trimethoxysilane, and the DP of each end group is 4, determined by the molar ratio of [3-(Methacryloyloxy) pro- pyl]trimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO 2 (BA 3 32-stat-MMA75)MEMO 2
  • the BA332-CO-MMA75 was synthesized in the first step. RAFT agent, butyl acrylate, methyl methacrylate, Plastomoll DNA and AIBN in amounts shown in Table 8 were added in initial charge. With N 2 bubbling for 30 minutes, the resulting mixture was then heated to 75 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 and feed 2 were added for 60 minutes and the polymerization was kept for 300 minutes. Then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 105 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 70%.
  • the conversions of butyl acrylate and methyl methacrylate in the first step are 90.5% and 100%, respectively.
  • the final conversions of butyl acrylate and MEMO are 95.1 % and 100%, respectively.
  • the telechelic polymer with a target number-average molecular weight (M n ) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the soft polymer backbone is poly (butyl acrylate), and the DP of it is 390, determined by the molar ratio of butyl acrylate to RAFT agent.
  • the functional silane groups are chain extended via acrylic acid (AA), and the DP of each end group is 3, determined by the molar ratio of acrylic acid to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: AA3 B A390 AA3.
  • the BA390 was synthesized in the first step. RAFT agent, butyl acetate, butyl acrylate and AIBN in amounts shown in Table 9 were added in initial charge. With N 2 bubbling for 30 minutes, the resulting mixture was then heated to 75 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 and feed 2 were added for 60 minutes, and the polymerization was kept for 300 minutes. Then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 345 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 70%.
  • the conversion of first step is 96.0%.
  • the final conversions of butyl acrylate and AA are 98.4% and 78.4%, respectively.
  • the polymer can be cured into a film by adding tris(acetylacetonato)aluminium as crosslinker in a molar ratio of Al 3+ to COOH group on the polymer of 0.75/1 to 1 .5/1 .
  • the crosslinkable random polymer with a target number-average molecular weight (M n ) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4-phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the random polymer was synthesized in one-pot. RAFT agent, butyl acrylate, ethyl acetate, MEMO and AIBN in amounts shown in Table 10 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 75 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 60 minutes, and the polymerization was kept for 240 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 75%.
  • the crosslinkable random polymer with a target number-average molecular weight (M n ) of 100,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4-phenylenebis(methylene) didodecyl dicarbonotrithioate.
  • the random polymer was synthesized in one-pot. RAFT agent, butyl acrylate, ethyl acetate, MEMO and AIBN in amounts shown in Table 11 were added in initial charge. With N 2 bubbling for 30 minutes, the resulting mixture was then heated to 75 °C to start polymerization under N 2 atmosphere. Under stirring, feed 1 was added for 60 minutes, and the polymerization was kept for 240 minutes. The solid content of final polymer solution is 65%.
  • the monomer conversions of butyl acrylate and MEMO are 97.4% and 100%, respectively.
  • VTMOS vinyltrimethoxysilane
  • Table 12 M n and PDI of polymer from Example 1 before and after aminolysis via EDA and VTMOS
  • Example 1 46,300, 1.30 47,700, 1.42
  • Example 13 (Comparative example):
  • Example 1 46,300, 1.30 51 ,100, 1.70
  • Table 14 M n and PDI of polymer from Example 7 before and after aminolysis via AMMO
  • Example 15 Elongation property in a basic formulation, by a manual stretching method
  • Formulation 25 parts by weight of polymer, 22 parts by weight of plasticizer (DINCH), 53 parts by weight of filler (CaCO 3 ) and 0.5 parts by weight of catalyst (phenyl phosphoric acid)
  • a typical curing procedure is as follows:
  • Random copolymers (Examples 10 and 11) generate very brittle samples after curing with worst elongation property.
  • the polymers with silane functional group precisely located on polymer terminal by the inventive process exhibit a significantly better elongation property.
  • Figure 1 shows sample's initial length and length before broken by a manual stretching method.
  • the sample in Figure 1 is from Example 6, which exhibits a 400% of tensile elongation at break.
  • Example 16 Mechanical properties in an optimized formulation, tested by ISO standard methods.
  • Formulation 26 parts by weight of polymer, 24 parts by weight of DINCH, 36 parts by weight of precipitated calcium carbonate (PCC), 12 parts by weight of ground calcium carbonate (GCC), 0.8 parts by weight of (3-aminopropyl)trimethoxysilane (AMMO), 0.8 parts by weight of VTMOS, 0.5 parts by weight of dibutyltin diacetate (DBTA)
  • a typical curing procedure is as follows:
  • Example 8 (a) 121%, 0.23 MPa (b) 173%, 0.44 MPa
  • Example 1 181%, 0.27 MPa (c) 170%, 0.57 MPa 10 min

Abstract

The present invention relates to a method for producing a terminal-functional polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization, a polymer obtained by this method and the use of said polymer for sealant or adhesive application, and a method for 5 RAFT end group removal.

Description

Method for producing a terminal-functional polymer
Field of the invention
The present invention relates to a method for producing a terminal-functional polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization, a polymer obtained by this method and the use of said polymer for sealant or adhesive application, and a method for RAFT end group removal.
Background of the invention
For sealant or adhesive market, “hybrid systems” are getting more and more attention recently. Such systems combine the properties of functional groups and soft polymer backbone to afford a number of advantages, e.g. high backbone flexibility and high elongation, excellent elongation recovery, good adhesion to various substates, low shrinkage, non-staining and paintable, and low VOC.
Functional polymers made by conventional free radical polymerization are known to suffer from poor mechanical property, as the functional groups are randomly distributed along the polymer backbone, leading to an ill-defined polymer network with many short polymer segments between neighboring crosslinking points. Polymers with functional group only on polymer terminals or close to terminals are known to enhance mechanical property of the materials after curing. The advent of controlled radical polymerization technology has allowed the synthesis of polymers where the functional groups are only placed on polymer terminals or close to polymer terminals. Reversible addition-fragmentation chain transfer (RAFT) polymerization is a well- established technology for making polymers with such tailored architecture.
US 2004220364A1 discloses a process of making telechelic silyl-terminated polyacrylates by using RAFT polymerization, with the following steps: (a) RAFT polymerization of acrylates, (b) converting RAFT end group into thiol group by aminolysis, and (c) end group functionalization by reacting terminal thiol group with isocyanate silane. The process disclosed in US 2004220364A1 involves one more step for polymer end group functionalization and has less than one silane group in each polymer terminal.
There is a need for a simple and easy to scale-up method towards the terminal-functional polymers having multiple functional groups on each polymer terminal, for example, precisely concentrated near polymer terminal.
Summary of the invention
The objective of the invention is to provide a simple synthetic route towards terminal-functional polymers, particularly silyl-terminated polymers, using RAFT polymerization.
Another objective of the invention is to provide a cheap and simple method for RAFT end group removal for silyl-terminated polymers.
Still another objective is to show the curability and advantageous mechanical properties of the resulting polymer, compared with random copolymer. Such properties are useful for sealant or adhesive applications.
In one aspect, the present invention relates to a method for producing a terminal-functional polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of at least one thiocarbonylthio group-containing compound, comprising the steps of
(a) polymerizing a radically polymerizable vinyl monomer to a conversion higher than 90%, and
(b) further polymerizing monomer carrying functional groups.
In another aspect, the present invention relates to a terminal-functional polymer, especially a silyl-terminated polymer obtained by the method according to the present invention.
In another aspect, the present invention relates to a sealant or adhesive composition, comprising the polymer according to the present invention.
In another aspect, the present invention relates to the use of the polymer according to the present invention for sealant or adhesive application.
In another aspect, the present invention relates to the removal of RAFT end group for silyl- terminated polymers, by aminolysis in the presence of silyl compounds.
In the method according to the present invention, the polymerization can be done in one-pot with no purification step needed in-between, and the number of terminal functional groups can be tuned to afford a required need for curing speed and density. The method according to the present invention is simple and cheap and easy to scale up. The terminal-functional polymer obtained by the method according to the present invention provides significantly improved elongation properties for sealant or adhesive applications.
Description of the drawing
Figure 1 shows sample's initial length and length before broken by a manual stretching method.
Detailed description of the invention
One aspect of the present invention relates to a method for producing a terminal-functional polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of at least one thiocarbonylthio group-containing compound, comprising the steps of
(a) polymerizing a radically polymerizable vinyl monomer to a conversion higher than 90%, and
(b) further polymerizing monomer carrying functional groups.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Expressions "a", "an", "the", when used to define a term, include both the plural and singular forms of the term.
All percentages, parts and ratios are by weight, unless otherwise specified. All such weights as they pertain to listed components are based on the specific ingredient level and, therefore, do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified. Vinyl Monomer
The vinyl monomer used in the present invention is not particularly limited as long as it is radically polymerizable. Examples of vinyl monomers which may be used include methacrylate esters, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2- hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1 ,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, tolyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-aminoethyl methacrylate, trifluoromethyl methacrylate, pentafluoroethyl methacrylate, and 2,2,2- trifluoroethyl methacrylate; acrylate esters, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, tolyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2- hydroxy propyl acrylate, stearyl acrylate, glycidyl acrylate, trifluoromethyl acrylate, pentafluoroethyl acrylate, 2,2,2-trifluoroethyl acrylate, 3-dimethylaminoethyl acrylate, isobutyl acrylate, 4-hydroxybutyl acrylate, tert-butyl acrylate, acrylate of alkyl-modified dipentaerythritol, Carbitol acrylate, acrylate of [epsilon]-caprolactone-modified dipentaerythritol, caprolactone- modified tetrahydrofurfuryl acrylate, diacrylate of caprolactone-modified neopentyl glycol hydroxypivalate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, trimethylolpropane ethoxy triacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, 1 ,9-nonandiol acrylate, 1 ,4-butanediol acrylate, 1 ,6-hexanediol acrylate, pentaerythritol triacrylate, 2- acryloyloxypropylhydrogen phthalate, methyl 3-methoxyacrylate, and allyl acrylate; aromatic alkenyl compounds, such as styrene, a-methylstyrene, p-methylstyrene, p-methoxystyrene, divinylbenzene, and vinylnaphthalene; vinyl cyanide compounds, such as acrylonitrile and methacrylonitrile; conjugated diene compounds, such as butadiene and isoprene; halogencontaining unsaturated compounds, such as vinyl chloride, vinylidene chloride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl bromide, and chloroprene; vinyl ester compounds, such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, divinyl carbonate, vinylethyl carbonate, and vinylphenyl carbonate; allyl ester compounds, such as allyl acetate, allyl propionate, allyl pivalate, allyl benzoate, allyl cinnamate, diallyl carbonate, allylmethyl carbonate, and allylphenyl carbonate; unsaturated group- containing ether compounds, such as vinyl phenyl ether, vinyl ethyl ether, divinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, 1 ,4-butanediol monovinyl ether, 1 ,4-butanediol divinyl ether, ethylene glycol monovinyl ether, ethylene glycol divinyl ether, propylene glycol monovinyl ether, propylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, vinyl glycidyl ether, allyl phenyl ether, allyl ethyl ether, diallyl ether, vinyl allyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1 ,4-butanediol monoallyl ether, 1 ,4-butanediol diallyl ether, ethylene glycol monoallyl ether, ethylene glycol diallyl ether, propylene glycol monoallyl ether, propylene glycol diallyl ether, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, polypropylene glycol monoallyl ether, polypropylene glycol diallyl ether, and allyl glycidyl ether; maleimide compounds, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; acrolein and methacrolein; cyclopolymerizable compounds, such as 1 ,6-heptadiene and diallylammonium salts; and N-vinyl pyrrolidone, N- vinyl carbazole, etc. These compounds may be used alone or in combination. When a copolymer is produced from a plurality of vinyl monomers, any form may be acceptable, such as a random copolymer, a block copolymer, a graft copolymer, or a combination of any of these.
Among the vinyl monomers described above, preferred are styrene, a-methylstyrene, vinyl chloride, vinylidene chloride, methacrylate esters, acrylate esters, methacrylonitrile, acrylonitrile, vinyl acetate, and maleimide compounds, more preferred are methacrylate esters and acrylate esters, and most preferred are methyl methacrylate, n-butyl acrylate, or a combination of these.
Thiocarbonylthio Group-containinq Compound
The thiocarbonylthio group-containing compound used in the present invention is at least one compound selected from the group consisting of a compound represented by general formula (I):
Figure imgf000005_0001
wherein
R is selected from the group consisting of alkyl, substituted alkyl, aralkyl, substituted aralkyl, a polyvalent aliphatic hydrocarbon group, a polyvalent aromatic hydrocarbon group, a polyvalent araliphatic hydrocarbon group, a polyvalent alipharomatic hydrocarbon group, a polyvalent aliphatic hydrocarbon group containing a heteroatom, and a polyvalent aromatic hydrocarbon group containing a heteroatom; preferably from the group consisting of phenyl, benzyl, 1- phenylethyl, 2-(2-phenyl)propyl, 1 -acetoxyethyl, 1-(4-methoxyphenyl)ethyl, ethoxycarbonylmethyl, 2-(2-ethoxycarbonyl)propyl, 2-(2-cyano)propyl, tert-butyl, 1 , 1 ,3,3- tetramethylbutyl, 2-[2-(p-chlorophenyl)]propyl, vinylbenzyl, tert-butylsulfide, 2-carboxylethyl, carboxylmethyl, cyanomethyl, 1 -cyanoethyl and 2-(2-cyano)butyl; and more preferably from the group consisting of phenyl, benzyl and 1 -phenylethyl;
Z is selected from the group consisting of alkyl, substituted alkyl, alkoxy, aryloxy, aryl, substituted aryl, aralkyl, substituted aralkyl, N-aryl-N-alkylamino, N,N-diarylamino, N,N- dialkylamino, thioalkyl, and dialkylphosphinyl; and preferably from the group consisting of C2- Ci6-alkyl, -S-C2-Ci6-alkyl, -O-C2-Ci6-alkyl, phenyl, benzyl, 4-chlorophenyl, 1-naphthyl, 2-naphthyl, diethoxyphosphinyl, thiomethyl (methylsulfide), phenoxy, thiophenyl, N,N-dimethylamino, N,N- diethylamino, N-phenyl-N-methylamino, N-phenyl-N-ethylamino, thiobenzyl and pentafluorophenoxy; more preferably from the group consisting of C2-Ci6-alkyl, -S-C2-Ci6-alkyl, and phenyl; and most preferably from the group consisting of Cs-Cu-alkyl, -S-Cs-Cu-alkyl, and phenyl; and p is an integer from 1 to 10, preferably from 2 to 8, more preferably from 2 to 4; and most preferably 2.
The thiocarbonylthio group-containing compounds used in the present invention may be used alone or in combination.
When the vinyl monomer used in the present invention is polymerized, the thiocarbonylthio group-containing compound must be present in the reaction system during polymerization. The addition method for the thiocarbonylthio group-containing compound is not particularly limited. In order to control the molecular weight and the molecular weight distribution of the polymer and in order to increase the introduction rate of functional groups, preferably, the thiocarbonylthio group-containing compound is dissolved or dispersed in the reaction system before polymerization is initiated. For example, in the case of solution polymerization, the thiocarbonylthio group-containing compound is preferably dissolved in a solvent or a vinyl monomer before addition.
The amount of the thiocarbonylthio group-containing compound used is not particularly limited. Since the degree of polymerization of the resultant polymer depends on the number of moles of the thiocarbonylthio group-containing compound added, the amount of the thiocarbonylthio group-containing compound may be calculated based on the required degree of polymerization or number-average molecular weight of the polymer.
Monomer Carrying Functional Groups
In one embodiment, the monomer carrying functional groups comprises at least one monomer having the formula (II):
Figure imgf000006_0001
wherein R1 is H or methyl and R2 represents or contains a crosslinkable functional group.
The crosslinkable functional group is not particularly restricted, but may include one or more of crosslinkable silyl, carboxyl, epoxy, hydroxyl and acrylamide groups, provided that when the vinyl monomer contains hydroxyl, the crosslinkable functional group is not hydroxyl.
Preferably, the monomer carrying silyl groups is at least one compound selected from the group consisting of a compound represented by general formula (11-1):
Figure imgf000007_0001
wherein R3 is H or methyl, Z1 is Ci-C4-alkylene, preferably propylene, each X is independently of one another -OCH3, -OCH2CH3 or -OCH2CH2CH3, and Y is H, -CH3, -OCH3, -OCH2CH3 or - OCH2CH2CH3.
More preferably, the monomer carrying silyl groups includes y- methacryloxypropyltrimethoxysilane, Y-methacryloxypropyltriethoxysilane, y- methacryloxypropyltripropoxysilane, y-methacryloxypropylmethyldimethoxysilane, y- methacryloxypropylmethyldiethoxysilane, y-methacryloxypropylmethyldipropoxysilane, methacryloxymethyldimethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, (methacryloxymethyl)-methyldimethoxysilane,
(methacryloxymethyl)-methyldiethoxysilane, y-acryloxypropyltrimethoxysilane, y- acryloxypropyltriethoxysilane, y-methacryloxymethyldiethoxysilane, y- acryloxypropyltripropoxysilane, y-acryloxypropylmethyldimethoxysilane, y- acryloxypropylmethyldiethoxysilane, y-acryloxypropylmethyldipropoxysilane, and the like.
The monomer carrying carboxyl groups includes, for example, unsaturated carboxylic acids containing from 3 to about 20 carbon atoms. The unsaturated carboxylic acids include, among others, acrylic acid, methacrylic acid, itaconic acid, beta carboxy ethyl acrylate, mono-2- acroyloxypropyl succinate, and the like.
The monomer carrying epoxy groups includes, for example, glycidyl methacrylate and glycidal acrylate. In certain embodiments, a particularly preferred epoxy functional monomer is commercially available under the designation S-100 from Synasia. That monomer is 3,4 epoxycydohexylmethyl methacrylate, [CAS 82428-30-6], having a chemical formula CHHI6O3 and a molecular weight of 196.2.
The monomer carrying acrylamide groups includes, for example, (meth)acrylamide and its derivatives including the N-substituted alkyl and aryl derivatives thereof. These include N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide and the like.
The monomer carrying hydroxyl groups includes, for example, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyethylcaprolactone(meth)acrylate and the like.
Polymerization Initiator
In the present invention, when vinyl monomers are radically polymerized in the presence of a thiocarbonylthio group-containing compound, the polymerization initiator or polymerization initiation method used is not particularly limited, and any polymerization initiator or polymerization initiation method commonly used in the art may be employed. Examples of polymerization initiators include, but are not limited to, peroxide polymerization initiators, such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1 ,1 ,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butyl-a-cumyl peroxide, di-a-cumyl peroxide, 1 ,4- bis[(tert-butylperoxy)isopropyl]benzene, 1 ,3-bis[(tert-butylperoxy)isopropyl]benzene, 2,5- dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne, 1 ,1- bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2- bis(tert-butylperoxy)butane, tert-butylperoxy acetate, tert-butylperoxy isobutylate, tertbutylperoxy octoate, tert-butylperoxy pivalate, tert-butylperoxy neodecanoate, tert-butylperoxy- 3,5,5-trimethyl hexanoate, tert-butylperoxy benzoate, tert-butylperoxy laurate, 2,5-dimethyl-2,5- bis(benzoylperoxy)hexane, bis(2-ethylhexyl)peroxy dicarbonate, diisopropylperoxy dicarbonate, di-sec-butylperoxy dicarbonate, di-n-propylperoxy dicarbonate, bis(3-methoxybutyl)peroxy dicarbonate, bis(2-ethoxyethyl)peroxy dicarbonate, bis(4-tert-butylcyclohexyl)peroxy dicarbonate, O-tert-butyl-O-isopropylperoxy carbonate, and succinic acid peroxide; azo polymerization initiators, such as 2,2'-azobis-(2-amidinopropane)dihydrochloride, 2,2'- azobis(dimethylisobutyrate), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'- azobis(isobutyronitrile), 1 ,1'-azobis(cyclohexane-1 -carbonitrile), azocumene, 2,2'-azobis(2- methylbutyronitrile), 2,2'-azobis-(2,4-dimethylvaleronitrile, 4,4'-azobis(4-cyanovaleric acid), 2- (tert-butylazo)-2-cyanopropane, 2,2'-azobis(2,4,4-trimethylpentane), and 2,2'-azobis(2- methylpropane); inorganic peroxides, such as potassium persulfate and sodium persulfate; vinyl monomers which thermally generate radical species, such as styrene; compounds which generate radical species by light, such as benzoin derivatives, benzophenone, acylphosphine oxide, and photo-redox systems; and redox polymerization initiators including sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, or the like, as a reducing agent, and potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, or the like, as an oxidizing agent. These polymerization initiators may be used alone or in combination. It may also be possible to use a polymerization initiation system by electron irradiation, X-ray irradiation, radiation irradiation, or the like. With respect to polymerization initiation methods, the methods described in Moad and Solomon "The Chemistry of Free Radical Polymerization", Pergamon, London, 1995, pp. 53-95 may be employed.
In the present invention, the amount of polymerization initiator used is not particularly limited. In order to produce a polymer with a narrow molecular weight distribution, the amount of radical species generated during polymerization is preferably 1 mole or less, and more preferably 0.5 moles or less, relative to 1 mole of thiocarbonylthio group in the thiocarbonylthio group- containing compound. In order to control the amount of radical species generated during polymerization, in addition to the control of the amount of the polymerization initiator, preferably, temperature is controlled in the case of the polymerization initiator which causes thermal dissociation, or the amount of energy is controlled in the case of the polymerization initiation system which generates radicals by light or electron beams. Because of ease of control of polymerization, using a polymerization initiator which causes thermal dissociation, the polymerization reaction is carried out preferably at temperatures which allow the polymerization initiator to have a half-life of 0.5 to 50 hours, more preferably at temperatures which allow the polymerization initiator to have a half-life of 1 to 20 hours, and most preferably at temperatures which allow the polymerization initiator to have a half-life of 5 to 15 hours.
Polymerization Media
The polymerization can be carried out in the presence of polymerization media.
The polymerization media can be solvents. Examples of solvents which may be used include, but are not limited to, hydrocarbon solvents, such as heptane, hexane, octane, and mineral spirit; ester solvents, such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, and diethylene glycol monobutyl ether acetate; ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; alcohol solvents, such as methanol, ethanol, isopropanol, n-butanol, secbutanol, and isobutanol; ether solvents, such as tetrahydrofuran, diethyl ether, dibutyl ether, dioxane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; and aromatic petroleum solvents, such as toluene, xylene, benzene, Swasol 310 (manufactured by Cosmo Oil Co., Ltd.), Swasol 1000 (manufactured by Cosmo Oil Co., Ltd.), and Swasol 1500 (manufactured by Cosmo Oil Co., Ltd.). These solvents may be used alone or in combination. The types and amounts of solvent used may be determined in consideration of the solubility of the monomers, the solubility of the resultant polymer, the polymerization initiator concentration and the monomer concentration suitable for achieving a satisfactory reaction rate, the solubility of the thiocarbonylthio group-containing compound, effects on human body and environment, availability, cost, etc., and are not particularly limited.
The polymerization media can be plasticizers. The plasticizer as used in accordance with the invention may comprise one or more selected from the group consisting of: phthalates, trimellitates, aliphatic dibasic esters, polyesters, polymeric, epoxides, phosphates.
In a preferred embodiment said plasticizer is selected from the group consisting of : butyl benzyl phthalate, butyl 2-ethylhexyl phthalate, diisohexyl phthalate, diiso-heptyl phthalate, di(2- ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, disononyl phthalate, diisodecyl phthalate, diiso undecyl phthalate, diisotredecyl phthalate, diiso (Cu, Ci2, C ) phthalate, di(n- butyl) phthalate, di(n-C7, C9) phthalate, di(n-C6, C8, Cw) phthalate, diiso(n-nonyl) phthalate, di(n- C7, C9, Cu) phthalate, di(n-C9, Cu) phthalate, di(n-undecyl) phthalate, tri(n-C8, Cw) trimellitate, tri(2-ethylhexyl) trimellitate, tri(isooctyl) trimellitate, tri(isononyl) trimellitate, di(n-C7, C9) adipate, di(2-ethylhexyl) adipate, di(isooctyl) adipate, di(isononyl) adipate, polyesters of adipinic acid or glutaric acid and propylene glycol or butylene glycol or 2,2-dimethyl-1 ,3-propanediol, epoxidized oils such as epoxidized soy bean oil, epoxidized linseed oil, epoxidized tall oil, octyl epoxy tal- late, 2-ethylhexyl epoxy tallate, Isodecyl di-phenyl phosphate, tri(2-ethylhexyl) phosphate, tricresyl phosphate, di(2-ethylhexyl) terephthalate, di(isononyl) cyclohexane- 1 ,2-dicarboxcylate and combinations thereof. In a particularly preferred embodiment said plasticizer is selected from the group consisting of: diisohexyl phthalate, diisoheptyl phthalate, di(2-ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, disononyl phthalate, diisodecyl phthalate, diiso undecyl phthalate, diisotredecyl phthalate, diiso (Cu, Ci2, Cw) phthalate, di(n-butyl) phthalate, di(n-C7, C9) phthalate, di(n-C6, C8, Cw) phthalate, diiso(n-nonyl) phthalate, di(n-C7, C9, Cu) phthalate, di(n-C9, Cu) phthalate, di(n-undecyl) phthalate, tri(n-C8, Cw) trimellitate, tri(2- ethylhexyl) trimellitate, tri(isooctyl) trimellitate, tri(isononyl) trimellitate, di(n-C7, C9) adipate, di(2- ethylhexyl) adipate, di(isooctyl) adipate, di(isononyl) adipate, polyesters of adipinic acid or glutaric acid and propylene glycol or butylene glycol or 2,2-dimethyl-1 ,3-propanediol, epoxidized oils such as epoxidized soy bean oil, di(isononyl) cyclohexane-1 ,2-dicarboxcylate and combinations thereof, preferably di(isononyl) adipate (e.g. Plastomoll DNA) and di(isononyl) cyclohexane- 1 ,2-dicarboxcylate (e.g. Hexamoll DINCH).
The polymerization can be carried out in batch, semi-batch, and continuous processes, preferably in semi-batch processes. In some preferred embodiments, polymerization temperature is about 60 to 90 °C, preferably about 65 to 80 °C. In some preferred embodiments, the total polymerization time is 3 to 15 h, preferably 4 to 10 h.
Step (c)/(c1)
In the present invention, the method for producing a terminal-functional polymer further comprises step (c) removing the RAFT end groups by aminolysis.
In the aminolysis, the thiocarbonylthio group-containing vinyl polymer is allowed to react with amine compounds.
The amine compounds include amines and their analogues. The amine compounds of the present invention also include amides and nitrogen-containing aromatic compounds which are analogous to amines. Examples of such amine compounds include, but are not limited to, hydroxylamine sulfate, hydroxylamine, N-(2-aminoethyl)ethanolamine, N-methylethanolamine, 12-aminododecanoic acid, 3-amino-1 -propanol, amine-modified acrylic polymers, allylamine, diallylamine, isopropylamine, diisopropylamine, 3,3'-iminobis(propylamine), ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, 3-(2-ethylhexyloxy)propylamine, 3- ethoxypropylamine, diisobutylamine, 3-(diethylamino)propylamine, di-2-ethylhexylamine, 3- (dibutylamino)propylamine, tert-butylamine, sec-butylamine, n-butylamine, n-propylamine, isopropylamine, 3-(methylamino)propylamine, 3-(dimethylamino)propylamine, N-methyl-3,3'- iminobis(propylamine), 3-methoxypropylamine, isopropanolamine, N-isopropylacrylamide, iminodiacetic acid, 3,3'-iminodipropionitrile, monoethanolamine, diethanolamine, N- ethylethylenediamine, ethyleneimine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-carboxy-4,4'-methylenebiscyclohexylamine, carbohydrazides, guanidine hydrochloride, guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate, aminoguanidine hydrochloride, aminoguanidine bicarbonate, guanylthiourea, guanylurea phosphate, guanylurea sulfate, glycylglycine, 2-chloroethylamine, 1 ,4-diaminobutane, 1 ,2-diaminopropane, 1 ,3-diaminopropane, diaminomaleonitrile, cyclohexylamine, cyclopentylamine, dicyandiamide, dicyclohexylamine, N-(3- (dimethylamino)propyl)acrylamide, N-(3-(dimethylamino)propyl)methacrylamide, dimethylamineborane, dimethylhydrazine, N,N'-ethylenebis(stearoamide), amide oleate, amide stearate, N,N'-methylenebis(stearoamide), methylol stearoamide, 3,9-bis(3-aminopropyl)- 2,4,8, 10-tetraoxaspiro[5,5]undecane, CTU guanamine, thiocarbohydrazide, thiosemicarbazide, thiourea, dihydrazide dodecanedioate, trans-1 ,2-cyclohexanediamine, dihydrazide adipate, dihydrazide sebacate, dihydrazide isophthalate, thiourea dioxide, 2- hydroxyethylaminopropylamine, isobutylamine, 2-bromoethylamine, hexamethylenediamine, 1 ,6-hexamethylenebis(N,N-dimethylsemicarbazide), n-hexylamine, polyethyleneimine, formamidine, formamidine acetate, formamide, methacrylamide, ammonia, monomethylamine, dimethylamine, trimethylamine, N,N'-methylenebis(acrylamide), N-methylolacrylamide, monomethylhydrazine, 3-(lauryloxy)propylamine, acetanilide, acetoacet-o-anisidide, acetoacetanilide, acetoacet-m-xylidide, acetoacet-o-chloroanilide, acetoacet-2,5,- dimethoxyanilide, acetoacet-2,5-dimethoxy-4-chloroanilide, acetoacet-o-toluidide, acetoacet-p- toluidide, o-anisidine, p-anisidine, aniline, p-aminoacetanilide, p-aminobenzoic acid, ethyl p- aminobenzoate ester, 2-amino-4-chlorophenol, 2-aminothiazole, 2-aminothiophenol, 2-amino-5- nitrobenzonitrile, o-aminophenol, m-aminophenol, p-aminophenol, p-aminobenzaldehyde, 4- aminobenzonitrile, anthranilic acid, 3-isopropoxyaniline, N-ethylaniline, N-ethylene toluene sulfonamide, 2,4-xylidine, 3,4-xylidine, m-xylylenediamine, p-cresidine, dianisidine, 4,4<1> - diaminostilbene-2,2'-disulfonic acid, 1 ,4-diaminoanthraquinone, 4,4'-diamino-3,3'- diethyldiphenylmethane, 4,4'-diaminobenzanilide, N,N-diethylaniline, diaminodiphenyl ether, diaminonaphthalene, diaminoanthracene, diphenylamine, dibenzylamine, N,N-dimethylaniline, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, sulfanilic acid, 1 , 1 , 1 ', 1 '-tetramethyl-4,4'- (methylenedi-p-phenylene)disemicarbazide, tobias acid, 2,4,5-trichloroaniline, o-tolidine, o- toluidine, m-toluidine, p-toluidine, m-toluylenediamine, sodium naphthionate, o-nitroaniline, m- nitroaniline, p-nitroaniline, o-nitro-p-chloroaniline, m-nitro-p-toluidine, o-chloro-p-toluidine-m- sulfonic acid, p-hydroxyphenylacetamide, 7-anilino-4-hydroxy-2-naphthalenesulfonic acid, phenylhydrazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, p- phenetidine, phenethylamine, benzylamine, benzophenone hydrazone, mesidine, metanilic acid, N-methylaniline, 2-methyl-4-nitroaniline, 2-methyl-4-methoxydiphenylamine, 2-amino-5- methylbenzenesulfonic acid, leuco-1 ,4-diaminoanthraquinone, paramine, p- hydroxyphenylglycine, acetaldehyde ammonia, acetoguanamine, 3-amino-1 , 2, 4-triazole, 2- aminopyridine, 3-aminopyridine, 4-aminopyridine, 1-(2-aminoethyl)piperazine, N-(3- aminopropyl)morpholine, 1-amino-4-methylpiperazine, isocyanuric acid, imidazole, 2- methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2- heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1- (cyanoethylaminoethyl)-2-methylimidazole, N-(2-(2-methyl-1-imidazolyl)ethyl)urea, 2,4-diamino- 6-(2-methyl-1-imidazolylethyl)-1 ,3,5-triazine, 2,4-diamino-6-(2-undecyl-1-imidazolylethyl)-1 ,3,5- tiazine, 2,4-diamino-6-(2-ethyl-4-methyl-1-imidazolylethyl)-1 ,3,5-tiazine, 2-phenyl-4-methyl-5- hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, an adduct of 2- methylimidazole and isocyanuric acid, an adduct of 2-phenylimidazole and isocyanuric acid, an adduct of 2,4-diamino-6-(2-methyl-1-imidazolylethyl)-1 ,3,5-triazine and isocyanuric acid, 2- methyl-4-formylimidazole, 2-phenyl-4-formylimidazole, 4-formylimidazole, 2,4-dimethyl-5- formylimidazole, 2,4-diphenyl-5-formylimidazole, 4-methylimidazole, 4-methyl-5- (hydroxymethyl)imidazole, 2-amino-4,5-dicyanoimdazole, imidazole-4,5-dicarboxylic acid, 3- carbamoyl-2-pyrazine carboxylic acid, imide succinate, quinaldine, quinoline, 1 ,3-di(4- piperidyl)propane, 2-imidazolidinone, 5,5-dimethylhydantoin, 2,5-dimethylpiperazine, cis-2,6- dimethylpiperazine, 3,5-dimethylpyrazole, 2-methyl-4-pyrazolone, 5,5'-bi-1 H-tetrazole, 5-phenyl- 1 H-tetrazole, 5-methyl-IH-tetrazole, 1 ,2,3,4-tetrahydroquinoline, bis(aminopropyl)piperazine, 1 ,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, hydantoin, (hydroxyethyl)piperazine, 2- pipecoline, 3-pipecoline, 4-pipecoline, 2-(1-piperazinyl)pyrimidine, piperazine, piperidine, pyrrolidine, pyrrole, phenylpyrazolidone, benzoguanamine, N-methylpiperazine, 2- methylpiperazine, 3-methyl-5-pyrazolone, 1-methylol-5,5-dimethylhydantoin, melamine, and morpholine.
Among them, when primary amines with a boiling point of 100 °C or less, such as methylamine and ethylamine, or secondary amines with a boiling point of 100 °C or less, such as dimethylamine and diethylamine, are used, excess amine compounds can be easily removed by distillation under reduced pressure, and thereby the purification step can be simplified, which is preferable.
When ammonia is used, as in primary or secondary amines with a boiling point of 100 °C or less, excess ammonia can be removed by distillation under reduced pressure, and thereby the purification step can be simplified, which is preferable.
In the present invention, the amount of amine compounds used is not particularly limited and preferably 0.5 to 1 ,000 moles, preferably 1 to 200 moles, more preferably 1 to 20 moles, and most preferably 1 to 10 moles, based on 1 mole of thiocarbonylthio group.
In the present invention, when the thiocarbonylthio group-containing vinyl polymer is treated with the amine compounds, the reaction conditions are not particularly limited. For example, a method in which the polymer is dissolved in an organic solvent, and the amine compound is added thereto; a method in which the amine compound is added to a water-based dispersion or emulsion; or a method in which the amine compound is directly added to the solid or molten polymer itself may be employed. The treatment temperature is not particularly limited. In view of reactivity and stability of the polymer, the treatment temperature is -50 °C to 300 °C, preferably - 10 °C to 200 °C, more preferably 10 °C to 100 °C, and most preferably 30 °C to 90 °C.
In one embodiment, the method for producing a silyl-terminated polymer further comprises step (c1) removing the RAFT end groups by aminolysis in the presence of a silane group-containing compound represented by general formula (III):
X1
R4— Si — X1 x1 (HD wherein R4 is C8-Ci6-alkyl, vinyl group, or C2-Ci0-alkyl substituted or interupted by one or more amine groups, and each X1 is independently of one another -OCH3, -OCH2CH3 or - OCH2CH2CH3.
In one preferred embodiment, R4 is C2-C -alkyl, prerferably C3-C8-alkyl, more prerferably C3-C6- alkyl, substituted or interupted by one or more amine groups, prerferably one, two or three amine groups, more prerferably one or two amine groups.
Examples of suitable silane group-containing compounds include vinyltrimethoxysilane, (3- aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2- aminoethyl)-N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, prerferably vinyltrimethoxysilane, (3-aminopropyl)trimethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. Another aspect of the present invention relates to a terminal-functional polymer, especially a silyl-terminated polymer obtained by the method according to the present invention.
Molecular Weight / Degree of Polymerization
In the present invention, the molecular weight of the resultant polymer is not particularly limited and is set depending on the application. In view of balance between workability and heat resistance, strength, or the like, the number-average molecular weight (Mn) determined by gel permeation chromatography (GPC) is in the range of 10,000 to 1 ,000,000, preferably in the range of 20,000 to 500,000, and more preferably in the range of 30,000 to 200,000. In the present invention, the molecular weight distribution of the resultant polymer is not particularly limited. Because of excellent workability and strength, the ratio (Mw/Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 3 or less, preferably 2 or less, and more preferably 1.5 or less.
In the present invention, the degree of polymerization for a radically polymerizable vinyl monomer is not particularly limited and is set depending on the number-average molecular weight (Mn). The degree of polymerization for monomer carrying functional groups is in the range of 1 .0 to 5, preferably in the range of 1 .2 to 4.
Another aspect of the present invention relates to a sealant or adhesive composition, comprising the polymer according to the present invention.
Catalyst
The sealant or adhesive composition according to the present invention may contain catalysts as necessary. Examples of the catalysts include, but are not limited to, titanate esters, such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds, such as dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; lead compounds, such as lead octylate; amine compounds, such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, and 1 ,3- diazabicyclo[5.4.6]undecene-7; carboxylate salts of these amine compounds; alkaline catalyst, such as potassium hydroxide, sodium hydroxide, sodium and potassium methylate; acid or acid salt such as a lower alkyl carboxylic acid (e.g. C2 to C6 carboxylic acid), such as acetic acid, valeric acid; a poly-carboxylic acid such as citric acid, malic acid, maleic acid, succinic acid, malonic acid, hippuric acid, tartaric acid, oxalic acid; a medium/long chain acid such as lauric acid, stearic acid; phosphoric acids such as phenyl phosphoric acid; any other acid such as levulinic acid, benzoic acid, boric acid, trifluoroacetic acid; organic bismuth compound, such as bismuth carboxylate, especially bismuth octoate, bismuth ethylhexanoate, bismuth neodecanoate or bismuth pivalate. These catalysts may be used alone or in combination.
In the sealant or adhesive composition according to the present invention, the amount of catalyst used is not particularly limited. Preferably, the catalyst is used in an amount of 0 to 10% by weight relative to the polymer according to the present invention.
Additive
The sealant or adhesive composition according to the present invention may also include one or more additives, such as those described below.
For example, in various embodiments, the composition includes Ultraviolet (UV) light absorbers selected from the group consisting of hydroxyphenylbenzotriazole, tris-aryl-s-triazine, hydroxybenzoate, 2-hydroxybenzophenone and cyanoacrylate ultraviolet light absorbers (UVAs).
In some embodiments, the UVA may include 5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)- 2H-benzotriazole, 2-(3,5-bis-a-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 4,6-diphenyl-2-(4- hexyloxy-2-hydroxyphenyl)-s-triazine, 4,6-bis-(2,4-dimethy|-,phenyl)-2-(2-hydroxy-4- octyloxyphenyl)-s-triazine, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate or 4-octyloxy-2- hydroxybenzophenone.
Many of the UVAs are commercial, for example TINUVIN 326, TINUVIN 234, TINUVIN 1577, TINUVIN 1600, CYASORB UV 1164, CYASORB THT, CYASORB UV 2908, CHIMASSORB 81 , UVINUL 3030, ADK LA-F70, ADK LA-1000, TINUVIN 400, etc.
Further, fillers based on magnesium silicate hydrate such as, for example, talc, based on aluminum hydroxide such as, for example, AI(OH)3, based on a feldspar, based on quartz powder and/or based on a calcium silicate and/or aluminum silicate may be used and may have a particle size from 1 to 20 micrometers. Adding one or more fillers may serve to improve the mechanical properties of the composition. In various embodiments, the fillers are chosen from calcium silicate, magnesium silicate hydrate, aluminum silicate, quartz powder and/or aluminum hydroxide such as, for example, aluminum trihydrate. Fillers based on CaCO3, TiO2, carbon black and/or BaSO4 as well as fillers with a significant Fe content and/or containing additional heavy metals may be used.
Lightweight fillers, in particular those based on polyurethane including their copolymers, polyamide wax and/or polyolefin wax may also be used. Lightweight fillers may also be used to reduce the density of the sealant or adhesive composition. Alternatively or additionally, hollow filing bodies may also be used.
Thixotropy agents, in particular based on feldspar, silicic acid/silica, fumed silica, sepiolite and/or bentonite may be used to adjust rheological properties, in particular for thixotropic behavior, of the composition.
Plasticizers, in particular based on an adipate, a benzoate, a citrate, a phthalate, a hydrogenated phthalate, an ester of a polyethylene glycol, and/or a terphenyl, preferably the same plasticizer used as polymerization media as decribed hereinabove, may be used, for example, to increase the flexibility of the sealant or adhesive composition.
Adhesion promoters may be used to improve the adhesion of the sealant or adhesive composition to a substrate. Examples of suitable adhesion promoters for improving adhesion include silane containing compounds, such as organosilanes, aminosilanes, epoxysilanes, amino alkoxy silanes, vinyl alkoxy silanes, isocyanato alkoxy silanes, isocyanurate functional alkoxy silanes, (meth)acrylic silanes, anhydridosilanes or adducts of the aforementioned silanes with primary aminosilanes, aminosilanes or urea silanes, polyamines such as polyethyleneimine, or combinations thereof. Specific examples of adhesion promoters can include vinyltriethoxysilane, vinyltrimethoxysilane, vinyl tris(2-methoxyethoxysilane), vinyl triisopropoxysilane, (meth)acryloyloxypropyl trimethoxy silane, y-(meth)acryloxypropyl trimethoxysilane, y-(meth)acryloxypropyl triethoxysilane, (3- methacryloxypropyl)-trimethoxysilane, (3-methacryloxypropyl)-triethoxy silane, (3- methacryloxypropyl)-triisopropoxy silane, 2-methyl-2-propenoic acid 3-[tris-(1-methylethoxy)- silyl]-propyl ester, (3-methacryloxypropyl)-methyldiethoxysilane, 3-glycidoxypropyl methyldiethoxy silane, 3-glycidoxypropylmethyldimethoxysilane, or a mixture thereof. In some examples, the organosilane comprises vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2- methoxyethoxysilane), vinyl triisopropoxysilane, gamma-methacryloxypropyltrimethoxy silane, or combinations thereof. For example, the organosilane can comprise vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma- isocyanato propyl trimethoxysilane, n-beta-(aminoethyl) gamma-aminopropyl trimethoxy silane, n-(2-aminoethyl)-3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl dimethoxy silane, bis-(gamma-trimethoxysilylpropyl amine), n-phenyl-gamma-aminopropyltrimethoxysilane, gamma-isocyanato propyl methyl dimethoxy silane, beta-(3,4-epoxycyclohexyl) ethyl triethoxy silane, gamma-glycidoxypropyltrimethoxysilane, (gamma-trimethoxysilylpropyl) isocyanurate, vinyltrimethoxysilane, vinyl triglycidoxyipropylmethylsilane, aminosilanes, or a combination thereof. In some embodiments, the adhesion promoter can include poly amines (i.e., polymers formed from either an amine-group containing monomer or an imine monomer as polymerized units such as aminoalkyl vinyl ether or sulfides; acrylamide or acrylic esters, such as dimethyl- aminoethyl(meth)acrylate; N-(meth)acryloxyalkyl-oxazolidines such as poly(oxazolidinylethyl methacrylate), N-(meth)acryloxyalkyltetrahydro-l,3-oxazines, and monomers that readily generate amines by hydrolysis). Suitable polyamines can include, for example, poly(oxazolidinylethyl methacrylate), poly(vinylamine), or polyalkyleneimine (e.g., polyethyleneimine).
In some embodiments, the amount of the adhesion promoter present in the compositions can be 0% by weight or greater (e.g., 1% by weight or greater, 2% by weight or greater, 3% by weight or greater, 4% by weight or greater, 5% by weight or greater, 6% by weight or greater, 8% by weight or greater, 10% by weight or greater, 12% by weight or greater, or 15% by weight or greater), based on the total weight of the composition.
Anti-aging agents may also be used, such as sterically hindered phenols, phenyleneamine and/or hindered amine light stabilizers such as 4,6-bis(dodecylthiomethyl)-o-cresol, ethylene- bis(oxyethylene)bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), thiodiethylene-bis(3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionate), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)-propionate) and/or phenylene amines such as, for example, N-isopropyl-N'- phenyl-p-phenylenediamine. Anti-aging agents may be used to scavenge the free radicals formed due to aging processes involving the composition and may contribute to delaying and/or preventing aging such as yellowing or embrittlement of the sealant or adhesive composition. Dehydrating agents, e.g. those based on an organofunctional alkoxysilane, based on a zeolite such as an alkali aluminum zeolite and/or based on a mono functional isocyanate may also be used.
Flame retardants, in particular those based on phosphate esters, based on ammonium polyphosphate, based on melamine, based on aluminum hydroxide and/or based on magnesium hydroxide may also be used to improve the fire prevention behavior of the sealant or adhesive composition such as, for example, to delay the onset of burning of the sealant or adhesive, to spontaneously terminate the burning process and/or to reduce the formation of smoke.
Vulcanization promoters may also be used, such as diphenylguanidine, thiuram, and/or sulfur (e.g. sulfur paste).
Whitening agent or colorant may also be used, such as TiO2, pigments and/or dyes.
In various embodiments, at least one organic solvent, in particular based on an ester and/or an ether such as, for example, ethyl acetate and/or monopropylene glycol monomethyl ether can be used.
Another aspect of the present invention relates to the use of the polymer according to the present invention for sealant or adhesive application.
The invention will now be described in more detail with the following examples which are given for purely illustrative purposes and which are not intended to limit the scope of the invention in any manner.
Examples
Materials:
Butyl acrylate (BA) is from Sigma. Plasticizers Hexamoll DINCH and Plastomoll DNA are BASF products. RAFT agent is from Boron Molecular (BM1812). For Example 15, CaCO3 is from Si- nopharm. Acid catalyst is from Islechem, LLC (M103). For Example 16, precipitated calcium carbonate (PCC) is from Guangxi Huana New Material Technology Co., Ltd (CCS-25, 80 nm). Ground calcium carbonate (GCC) is Omycarb 5 (5 pm). Organotin catalyst (dibutyltin diacety- lacetonate, DBTA) is from Nitto Kasei Co., Ltd (U-220H). All other reagents are from Sinopharm.
Target number-average molecular weight (Mn)
Theoretical number-average molecular weight (Mn) of a polymer synthesized can be estimated by the following eguation:
[Monomer] * M(mon)
Mn = 1 - r rn - ~ * C% + M(RAFT) wherein [Monomer] and [RAFT] are concentrations (mol/L) of monomer and RAFT agent, respectively. C% is the monomer conversion. M(mon) and M(RAFT) are molecular weights of monomer and RAFT agent, respectively.
Target number-average molecular weight (Mn) is the theoretical Mn estimated by above eguation when assuming monomer conversion (C%) is 100%.
GPC Measurement
Molecular weight and polydispersity of polymers are determined by gel permeation chromatography (GPC) using PSS SDV 10e5/10e4/10e3 columns (300*8 nm) and THF as eluent. The polymers are dissolved in THF at 1.5 mg/mL for 12 h at room temperature, filtered by 0.45 pm membrane before injection. The molecular weight is calibrated by conventional GPC against polystyrene (PS) standards.
Example 1 :
The telechelic polymer with a target number-average molecular weight (Mn) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate. The soft polymer backbone is poly (butyl acrylate), and the target DP of it is 390 in case of 100% monomer conversion, determined by the molar ratio of butyl acrylate to RAFT agent. The functional silane groups are chain extended via 3-(trimethoxysilyl) propyl acrylate (TSPA), and the DP of each end group is 2, determined by the molar ratio of 3-(trimethoxysilyl)propyl acrylate to 2 times of RAFT agent (two polymer terminals in one chain). Therefore, the telechelic polymer has a target chemical formula: TSPA2BA390TSPA2.
The BA390 was synthesized in the first step. RAFT agent, butyl acrylate and Hexamoll DINCH in amounts shown in Table 1 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 68 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 150 minutes, feed 2 for 180 minutes, and the polymerization was kept for 210 minutes. The reaction was heated to 75 °C, then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 135 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 85%.
Table 1 : Semi-batch synthesis of TSPA2BA390TSPA2
Initial charge 36.5 g of Hexamoll DINCH, 2.64 g of RAFT agent, 40 g of butyl acrylate
Feed 1 160 g of butyl acrylate
Feed 2 9.94 g of WAKO V65 (1% solution in ethyl acetate)
Feed 3 3.75 g of TSPA
Feed 4 12.42 g of WAKO V65 (1% solution in ethyl acetate)
According to 1H NMR, the monomer conversion of the first step is 95.0%. After chain extension with TSPA, the final monomer conversion overall is 98.6%. The resulting polymer has a numberaverage molecular weight (Mn) of 46,300 g/mol, PDI=1.30, determined by GPC.
Example 2:
The telechelic polymer with a target number-average molecular weight (Mn) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate. The soft polymer backbone is poly (butyl acrylate), and the DP of it is 390, determined by the molar ratio of butyl acrylate to RAFT agent. The functional silane groups are chain extended via [3- (Methacryloyloxy)propyl]trimethoxysilane (MEMO), and the DP of each end group is 2, determined by the molar ratio of [3-(Methacryloyloxy)propyl]trimethoxysilane to 2 times of RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO2BA390MEMO2.
The BA390 was synthesized in the first step. RAFT agent, butyl acrylate and ethyl acetate in amounts shown in Table 2 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 68 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 150 minutes, feed 2 for 180 minutes, and the polymerization was kept for 210 minutes. The reaction was heated to 75 °C, then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 135 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 85%.
Table 2: Semi-batch synthesis of MEMO2BA390MEMO2
Initial charge 25.5 g of ethyl acetate, 2.64 g of RAFT agent, 40 g of butyl acrylate
Feed 1 160 g of butyl acrylate
Feed 2 9.94 g of WAKO V65 (1% solution in ethyl acetate)
Feed 3 3.98 g of MEMO
Feed 4 12.42 g of WAKO V65 (1% solution in ethyl acetate)
According to 1H NMR, the conversion of the first step is 95.4%. After chain extension with MEMO, the final conversions of butyl acrylate and MEMO are 98.2% and 91.0%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 48,900 g/mol, PDI=1.27, determined by GPC.
Example 3:
The telechelic polymer with a target number-average molecular weight (Mn) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate. The soft polymer backbone is poly (butyl acrylate), and the DP of it is 390, determined by the molar ratio of butyl acrylate to RAFT agent. The functional silane groups are chain extended via 3- Methacryloxypropylmethyldimethoxysilane (MEDMO), and the DP of each end group is 2, determined by the molar ratio of 3-Methacryloxypropylmethyldimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEDMO2BA390MEDMO2.
The BA390 was synthesized in the first step. RAFT agent, butyl acrylate and ethyl acetate in amounts shown in Table 3 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 76 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 150 minutes, feed 2 for 180 minutes, and the polymerization was kept for 210 minutes. Then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 135 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 85%. Table 3: Semi-batch synthesis of MEDMO2BA390MEDMO2
Initial charge 23.5 g of ethyl acetate, 3.43 g of RAFT agent, 52 g of butyl acrylate
Feed 1 208 g of butyl acrylate
Feed 2 8.54 g of AIBN (1% solution in ethyl acetate)
Feed 3 3.67 g of 3-Methacryloxypropylmethyldimethoxysilane
Feed 4 10.68 g of AIBN (1% solution in ethyl acetate)
According to 1H NMR, the conversion of the first step is 95.2%. After chain extension with MEDMO, the final conversions of butyl acrylate and MEDMO are 99.6% and 100%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 45,300 g/mol, PDI=1.50, determined by GPC.
Example 4:
The telechelic polymer with a target number-average molecular weight (Mn) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate. The soft polymer backbone is poly (butyl acrylate), and the DP of it is 390, determined by the molar ratio of butyl acrylate to RAFT agent. The functional silane groups are chain extended via [3-(Methacryloyloxy) pro- pyl]trimethoxysilane, and the DP of each end group is 4, determined by the molar ratio of [3- (Methacryloyloxy)propyl]trimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO4BA390MEMO4.
The BA390 was synthesized in the first step. RAFT agent, butyl acrylate and ethyl acetate in amounts shown in Table 4 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 68 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 150 minutes, feed 2 for 180 minutes, and the polymerization was kept for 210 minutes. The reaction was heated to 75 °C, then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 135 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 85%.
Table 4: Semi-batch synthesis of MEMO4BA390MEMO4
Initial charge 25.5 g of ethyl acetate, 2.64 g of RAFT agent, 40 g of butyl acrylate
Feed 1 160 g of butyl acrylate
Feed 2 9.94 g of WAKO V65 (1% solution in ethyl acetate)
Feed 3 3.98 g of MEMO
Feed 4 12.42 g of WAKO V65 (1% solution in ethyl acetate)
According to 1H NMR, the conversion of the first step is 96.5%. After chain extension with MEMO, the final conversions of butyl acrylate and MEMO are 97.8% and 73.8%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 45,300 g/mol, PDI=1.80, determined by GPC. Example 5:
The telechelic polymer with a target number-average molecular weight (Mn) of 100,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate. The soft polymer backbone is poly (butyl acrylate), and the DP of it is 780, determined by the molar ratio of butyl acrylate to RAFT agent. The functional silane groups are chain extended via [3-(Methacryloyloxy) pro- pyl]trimethoxysilane, and the DP of each end group is 4, determined by the molar ratio of [3- (Methacryloyloxy)propyl]trimethoxysilane to 2 times of RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO4BA780MEMO4.
The BA7SO was synthesized in the first step. RAFT agent, butyl acrylate, Plastomoll DNA and AIBN in amounts shown in Table 5 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 70 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 60 minutes and the polymerization was kept for 240 minutes. Then feed 2 was added for 15 minutes and the polymerization was kept for 285 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 65%.
Table 5: Semi-batch synthesis of MEMO4BA780MEMO4
Initial charge 45 g of Plastomoll DNA, 1.39 g of RAFT agent, 105 g of butyl acrylate, 0.01 g of AIBN
Feed 1 105 g of butyl acrylate, 45 g of Plastomoll DNA, 0.08 g of AIBN
Feed 2 4.18 g of MEMO, 26 g of Plastomoll DNA, 0.09 g of AIBN
According to 1H NMR, the conversion of first step is 91.4%. After chain extension with MEMO, the final conversions of butyl acrylate and MEMO are 98.1% and 100%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 81 ,900 g/mol, PDI=1.84, determined by GPC.
Example 6:
The telechelic polymer with a target number-average molecular weight (Mn) of 70,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate. The soft polymer backbone is poly (butyl acrylate), and the DP of it is 546, determined by the molar ratio of butyl acrylate to RAFT agent. The functional silane groups are chain extended via [3-(Methacryloyloxy) propyl] trimethoxysilane, and the DP of each end group is 4, determined by the molar ratio of [3- (Methacryloyloxy)propyl]trimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO4BA546MEMO4.
The BA546 was synthesized in the first step. RAFT agent, butyl acrylate, Plastomoll DNA and AIBN in amounts shown in Table 6 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 70 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 60 minutes and the polymerization was kept for 240 minutes. Then feed 2 was added for 15 minutes and the polymerization was kept for 285 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 70%.
Table 6: Semi-batch synthesis of MEMO4BA546MEMO4
Initial charge 42 g of Plastomoll DNA, 1.91 g of RAFT agent, 100 g of butyl acrylate, 0.007 g of AIBN
Feed 1 100 g of butyl acrylate, 42 g of Plastomoll DNA, 0.07 g of AIBN
Feed 2 5.78 g of MEMO, 5 g of Plastomoll DNA, 0.12 g of AIBN
In the first step, the conversion of first step is 93.22%. After chain extension with MEMO, the final conversions of butyl acrylate and MEMO are 98.39% and 100%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 60,000 g/mol, PDI=1.65, determined by GPC.
Example 7:
The telechelic polymer with a target number-average molecular weight (Mn) of 40,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate. The soft polymer backbone is poly (butyl acrylate), and the DP of it is 312, determined by the molar ratio of butyl acrylate to RAFT agent. The functional silane groups are chain extended via [3-(Methacryloyloxy) propyl] trimethoxysilane, and the DP of each end group is 1.2, determined by the molar ratio of [3- (Methacryloyloxy) propyl]trimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO12BA312MEMO12.
The BA312 was synthesized in the first step. RAFT agent and Hexamoll DINCH in amounts shown in Table 7 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 76 °C under N2 atmosphere. Under stirring, feed 1 was added for 90 minutes, feed 2 for 120 minutes, and the polymerization was kept for 210 minutes. Then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 75 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 90%.
Table 7: Semi-batch synthesis of MEMO12BA312MEMO12
Initial charge 32.5 g of Hexamoll DINCH, 4.62 g of RAFT agent
Feed 1 280 g of butyl acrylate
Feed 2 17.4 g of WAKO V65 (1% solution in ethyl acetate)
Feed 3 4.17 g of MEMO
Feed 4 21.74 g of WAKO V65 (1% solution in ethyl acetate)
According to 1H NMR, the conversion of first step is 96.7%. After chain extension with MEMO, the final conversions of butyl acrylate and MEMO are 98.6% and 100%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 39,700 g/mol, PDI=1.24, determined by GPC. Example 8:
The telechelic polymer with a target number-average molecular weight (Mn) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate. The soft polymer backbone is a statistical copolymer of butyl acrylate (DP=332) and methyl methacrylate (DP=75), determined by the molar ratio of butyl acrylate and methyl methacrylate to RAFT agent. The functional silane groups are chain extended via [3-(Methacryloyloxy) propyl] trimethoxysilane, and the DP of each end group is 4, determined by the molar ratio of [3-(Methacryloyloxy) pro- pyl]trimethoxysilane to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: MEMO2(BA332-stat-MMA75)MEMO2
The BA332-CO-MMA75 was synthesized in the first step. RAFT agent, butyl acrylate, methyl methacrylate, Plastomoll DNA and AIBN in amounts shown in Table 8 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 75 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 and feed 2 were added for 60 minutes and the polymerization was kept for 300 minutes. Then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 105 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 70%.
Table 8: Semi-batch synthesis of MEMO2(BA332-stat-MMA75)MEMO2
Initial charge 33 g of Hexamoll DINCH, 85 g of butyl acrylate, 2.63 g of RAFT agent, 15 g of methyl methacrylate, 0.82 g of AIBN (1 % solution in ethyl acetate)
Feed 1 85 g of butyl acrylate, 33 g of Hexamoll DINCH, 15 g of methyl methacrylate
Feed 2 7.38 g of AIBN (1 % solution in ethyl acetate)
Feed 3 2.37 g of MEMO, 10.93 g of Hexamoll DINCH
Feed 4 2.5 g of AIBN (1 % solution in ethyl acetate)
According to 1H NMR, the conversions of butyl acrylate and methyl methacrylate in the first step are 90.5% and 100%, respectively. After chain extension with MEMO, the final conversions of butyl acrylate and MEMO are 95.1 % and 100%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 41 ,000 g/mol, PDI=1.30, determined by GPC.
Example 9:
The telechelic polymer with a target number-average molecular weight (Mn) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4- phenylenebis(methylene) didodecyl dicarbonotrithioate.
The soft polymer backbone is poly (butyl acrylate), and the DP of it is 390, determined by the molar ratio of butyl acrylate to RAFT agent. The functional silane groups are chain extended via acrylic acid (AA), and the DP of each end group is 3, determined by the molar ratio of acrylic acid to 2 times RAFT agent. Therefore, the telechelic polymer has a target chemical formula: AA3 B A390 AA3.
The BA390 was synthesized in the first step. RAFT agent, butyl acetate, butyl acrylate and AIBN in amounts shown in Table 9 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 75 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 and feed 2 were added for 60 minutes, and the polymerization was kept for 300 minutes. Then feed 3 and feed 4 were added for 15 minutes and the polymerization was kept for 345 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 70%.
Table 9: Semi-batch synthesis of AA3BA390AA3
Initial charge 100 g of butyl acrylate, 2.64 g of RAFT agent, 30 g of butyl acetate, 0.82 g of AIBN (1 % solution in ethyl acetate)
Feed 1 100 g of butyl acrylate
Feed 2 17.4 g of AIBN (1 % solution in ethyl acetate)
Feed 3 1.73 g of AA, 10 g of butyl acetate
Feed 4 10.95 g of AIBN (1 % solution in ethyl acetate)
According to 1H NMR, the conversion of first step is 96.0%. After chain extension with AA, the final conversions of butyl acrylate and AA are 98.4% and 78.4%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 52,000 g/mol, PDI=1.38, determined by GPC.
The polymer can be cured into a film by adding tris(acetylacetonato)aluminium as crosslinker in a molar ratio of Al3+ to COOH group on the polymer of 0.75/1 to 1 .5/1 .
Example 10 (Comparative example):
The crosslinkable random polymer with a target number-average molecular weight (Mn) of 50,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4-phenylenebis(methylene) didodecyl dicarbonotrithioate.
The random polymer was synthesized in one-pot. RAFT agent, butyl acrylate, ethyl acetate, MEMO and AIBN in amounts shown in Table 10 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 75 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 60 minutes, and the polymerization was kept for 240 minutes. Residual monomer was removed by evaporation. The solid content of final polymer solution is 75%.
Table 10: Semi-batch synthesis of crosslinkable random polymer with Mn=50,000
Initial charge 36 g of ethyl acetate, 1.58 g of RAFT agent, 120 g of butyl acrylate,
4.77 g of MEMO, 0.67 g of AIBN (1% solution in ethyl acetate)
Feed 1 5.91 g of AIBN (1 % solution in ethyl acetate) According to 1H NMR, the monomer conversions of butyl acrylate and MEMO are 96.9% and 100%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 48,600 g/mol, PDI=1.42, determined by GPC.
Example 11 (Comparative example):
The crosslinkable random polymer with a target number-average molecular weight (Mn) of 100,000 g/mol was synthesized with semi-batch process in one-pot with a bis-symmetric RAFT agent 1 ,4-phenylenebis(methylene) didodecyl dicarbonotrithioate.
The random polymer was synthesized in one-pot. RAFT agent, butyl acrylate, ethyl acetate, MEMO and AIBN in amounts shown in Table 11 were added in initial charge. With N2 bubbling for 30 minutes, the resulting mixture was then heated to 75 °C to start polymerization under N2 atmosphere. Under stirring, feed 1 was added for 60 minutes, and the polymerization was kept for 240 minutes. The solid content of final polymer solution is 65%.
Table 11 : Semi-batch synthesis of crosslinkable random polymer with Mn=100,000
Initial charge 60 g of ethyl acetate, 0.79 g of RAFT agent, 120 g of butyl acrylate,
2.39 g of MEMO, 0.66 g of AIBN (1% solution in ethyl acetate)
Feed 1 5.91 g of AIBN (1% solution in ethyl acetate)
According to 1H NMR, the monomer conversions of butyl acrylate and MEMO are 97.4% and 100%, respectively. The resulting polymer has a number-average molecular weight (Mn) of 81 ,200 g/mol, PDI=2.09, determined by GPC.
Aminolysis
Example 12:
The procedure for aminolysis of silyl-terminated polybutylacrylate via ethylenediamine (EDA) and vinyltrimethoxysilane (VTMOS):
1 . Preparing initial charge: diluting polymer from Example 1 to 70% via propionitrile (EtCN)
2. Adding vinyltrimethoxysilane (VTMOS) equal to 2 wt.% of pure polymer
3. Under N2, heated to 50 °C
4. Adding EDA, molar ratio of [EDA]/[trithioester]=3/1
5. Keeping reaction 1 h and cooled to room temperature (RT),
6. Transferring the sample to flask and removing solvent and ethylenediamine by rotary evaporation: 1 h at 40 °C + 1 h at 70 °C. Cooled down to RT to obtain final product.
Table 12: Mn and PDI of polymer from Example 1 before and after aminolysis via EDA and VTMOS
Polymer from Example _ Before aminolysis (Mn, PDI) After aminolysis (Mn, PDI)
Example 1 46,300, 1.30 47,700, 1.42 Example 13 (Comparative example):
The procedure for aminolysis of silyl-terminated polybutylacrylate via EDA:
1 . Preparing initial charge: diluting polymer from Example 1 to 70% via EtCN
2. Under N2, heated to 50 °C
3. Adding EDA, molar ratio of [EDA]/[trithioester]=3/1
4. Keeping reaction for 1 h and cooled to room temperature,
5. Transferring the sample to flask and removing solvent and ethylenediamine by rotary evaporation at 50 °C. Cooled down to RT to obtain final product.
Table 13: Mn and PDI of polymer from Example 1 before and after aminolysis via EDA
Polymer from Example _ Before aminolysis (Mn, PDI) After aminolysis (Mn, PDI)
Example 1 46,300, 1.30 51 ,100, 1.70
When removing the RAFT end groups by aminolysis, amine will catalyze silane hydrolysis and condensation. But this issue was suppressed by performing the aminolysis with VTMOS, as reflected by smaller PDI of Example 12 compared with Example 13 after aminolysis.
Example 14:
The procedure for aminolysis of silyl-terminated polybutylacrylate via (3- aminopropyl)trimethoxysilane (AMMO)
1 . Preparing initial charge: original polymer solution from Example 7.
2. Under N2, heated to 80 °C
3. Adding AMMO, molar ratio of [AMMO]/[trithioester]=10/1 , keeping reaction 1 h
4. Cooled to room temperature
5. Transferring the sample to flask and removing solvent by rotary evaporation at 50 °C. Cooled down to RT to obtain final product.
Table 14: Mn and PDI of polymer from Example 7 before and after aminolysis via AMMO
Polymer from Example _ Before aminolysis (Mn, PDI) After aminolysis (Mn, PDI)
Example 7 45,400, 1.37 43,800, 1.45
Application Examples
Example 15. Elongation property in a basic formulation, by a manual stretching method
Formulation: 25 parts by weight of polymer, 22 parts by weight of plasticizer (DINCH), 53 parts by weight of filler (CaCO3) and 0.5 parts by weight of catalyst (phenyl phosphoric acid)
A typical curing procedure is as follows:
1 . Blending polymer and plasticizer to ensure good flowability
2. Mixing CaCO3
3. Adding catalyst and mixing it for 1 min. Tensile elongation at break (Eb) by a manual stretching method: taking a sample with initial length of Lo and slowly stretching the two ends with a speed of 20 mm/min until broken. The final length of the sample (L) before broken is recorded by a ruler. The tensile elongation at break (Eb) is defined by the following equation:
Eb = (L-Lo)/Lo*1 OO%
Table 15: Tensile elongation at break of polymers from some of the above Examples
Figure imgf000026_0001
Random copolymers (Examples 10 and 11) generate very brittle samples after curing with worst elongation property. In contrast, the polymers with silane functional group precisely located on polymer terminal by the inventive process exhibit a significantly better elongation property.
Figure 1 shows sample's initial length and length before broken by a manual stretching method. The sample in Figure 1 is from Example 6, which exhibits a 400% of tensile elongation at break.
Example 16: Mechanical properties in an optimized formulation, tested by ISO standard methods.
Mechanical properties of the cured sample are measured by following standard and instrument: Dumbbell-shape sample: ISO 527, Zwick Z010
H-shape sample. :ISO 8339, Zwick Z010
Formulation: 26 parts by weight of polymer, 24 parts by weight of DINCH, 36 parts by weight of precipitated calcium carbonate (PCC), 12 parts by weight of ground calcium carbonate (GCC), 0.8 parts by weight of (3-aminopropyl)trimethoxysilane (AMMO), 0.8 parts by weight of VTMOS, 0.5 parts by weight of dibutyltin diacetate (DBTA)
A typical curing procedure is as follows:
1 . Blending polymer and DINCH to ensure good flowability.
2. Mixing PCC, GCC, VTMOS and AMMO in sequence (water content: ~900 ppm)
3. Putting mixture into speed mixer under vacuum atmosphere for 10 min (water content: ~130 ppm).
4. Adding catalyst DBTA and mixing it under vacuum atmosphere for 1 min.
5. Sealing and packing.
Curing is done in a humidity control room (23 °C, 50% RH). The elongation is evaluated by instrument at 15 days after curing. Table 16: Mechanical properties of polymers from some of the above Examples
Polymer from H-shape (tensile Dumbbell (tensile elon- Skin formation time
Example elongation at break, gation at break, maximaximum tensile mum tensile strength) strength)
Kaneka XMAP 110S 208%, 0.33 MPa(c) 216%, 0.60 MPa 30 min
Kaneka XMAP 100S(a) 66%, 0.61 MPa<b» 106%, 1.00 MPa
Example 8(a) 121%, 0.23 MPa(b) 173%, 0.44 MPa
Example 1 181%, 0.27 MPa(c) 170%, 0.57 MPa 10 min
Example 2 170%, 0.39 MPa® 139%, 0.52 MPa 10 min
Example 12 171%, 0.18 MPa(c) 152%, 0.44 MPa 5 min
Example 12<a» 261%, 0.48 MPa
(a) These samples are catalyzed with a Borchi Kat 24 catalyst (Bismuth tris(2-ethylhexanoate))
(b) These tests use anodized aluminum as substrate. (c) These tests use glass as substrate.
A good mechanical property (tensile elongation and tensile strength) is maintained after aminolysis (Example 12).

Claims

27 Claims
1. A method for producing a terminal-functional polymer by reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of at least one thiocarbonylthio group- containing compound, comprising the steps of (a) polymerizing a radically polymerizable vinyl monomer to a conversion higher than 90%, and (b) further polymerizing monomer carrying functional groups.
2. The method according to claim 1 , wherein the thiocarbonylthio group-containing compound is at least one compound selected from the group consisting of a compound represented by general formula (I):
Figure imgf000028_0001
wherein
R is selected from the group consisting of alkyl, substituted alkyl, aralkyl, substituted aralkyl, a polyvalent aliphatic hydrocarbon group, a polyvalent aromatic hydrocarbon group, a polyvalent araliphatic hydrocarbon group, a polyvalent alipharomatic hydrocarbon group, a polyvalent aliphatic hydrocarbon group containing a heteroatom, and a polyvalent aromatic hydrocarbon group containing a heteroatom; preferably from the group consisting of phenyl, benzyl, 1- phenylethyl, 2-(2-phenyl)propyl, 1 -acetoxyethyl, 1-(4-methoxyphenyl)ethyl, ethoxycarbonylmethyl, 2-(2-ethoxycarbonyl)propyl, 2-(2-cyano)propyl, tert-butyl, 1 , 1 ,3,3- tetramethylbutyl, 2-[2-(p-chlorophenyl)]propyl, vinylbenzyl, tert-butylsulfide, 2-carboxylethyl, carboxylmethyl, cyanomethyl, 1 -cyanoethyl and 2-(2-cyano)butyl; and more preferably from the group consisting of phenyl, benzyl and 1 -phenylethyl;
Z is selected from the group consisting of alkyl, substituted alkyl, alkoxy, aryloxy, aryl, substituted aryl, aralkyl, substituted aralkyl, N-aryl-N-alkylamino, N,N-diarylamino, N,N- dialkylamino, thioalkyl, and dialkylphosphinyl; and preferably from the group consisting of C2- Ci6-alkyl, -S-C2-Ci6-alkyl, -O-C2-Ci6-alkyl, phenyl, benzyl, 4-chlorophenyl, 1-naphthyl, 2-naphthyl, diethoxyphosphinyl, thiomethyl (methylsulfide), phenoxy, thiophenyl, N,N-dimethylamino, N,N- diethylamino, N-phenyl-N-methylamino, N-phenyl-N-ethylamino, thiobenzyl and pentafluorophenoxy; more preferably from the group consisting of C2-Ci6-alkyl, -S-C2-Ci6-alkyl, and phenyl; and most preferably from the group consisting of Cs-Cu-alkyl, -S-Cs-Cu-alkyl, and phenyl; and p is an integer from 1 to 10, preferably from 2 to 8, more preferably from 2 to 4; and most preferably 2.
3. The method according to claim 1 or 2, wherein the vinyl monomer includes methacrylate esters, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2- hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1 ,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, tolyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-aminoethyl methacrylate, trifluoromethyl methacrylate, pentafluoroethyl methacrylate, and 2,2,2- trifluoroethyl methacrylate; acrylate esters, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, tolyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2- hydroxyethyl acrylate, 2- hydroxy propyl acrylate, stearyl acrylate, glycidyl acrylate, trifluoromethyl acrylate, pentafluoroethyl acrylate, 2,2,2-trifluoroethyl acrylate, 3-dimethylaminoethyl acrylate, isobutyl acrylate, 4-hydroxybutyl acrylate, tert-butyl acrylate, acrylate of alkyl-modified dipentaerythritol, Carbitol acrylate, acrylate of [epsilon]-caprolactone-modified dipentaerythritol, caprolactone- modified tetrahydrofurfuryl acrylate, diacrylate of caprolactone-modified neopentyl glycol hydroxypivalate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, trimethylolpropane ethoxy triacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, 1 ,9-nonandiol acrylate, 1 ,4-butanediol acrylate, 1 ,6-hexanediol acrylate, pentaerythritol triacrylate, 2- acryloyloxypropylhydrogen phthalate, methyl 3-methoxyacrylate, and allyl acrylate; aromatic alkenyl compounds, such as styrene, a-methylstyrene, p-methylstyrene, p-methoxystyrene, divinylbenzene, and vinylnaphthalene; vinyl cyanide compounds, such as acrylonitrile and methacrylonitrile; conjugated diene compounds, such as butadiene and isoprene; halogencontaining unsaturated compounds, such as vinyl chloride, vinylidene chloride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl bromide, and chloroprene; vinyl ester compounds, such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, divinyl carbonate, vinylethyl carbonate, and vinylphenyl carbonate; allyl ester compounds, such as allyl acetate, allyl propionate, allyl pivalate, allyl benzoate, allyl cinnamate, diallyl carbonate, allylmethyl carbonate, and allylphenyl carbonate; unsaturated group- containing ether compounds, such as vinyl phenyl ether, vinyl ethyl ether, divinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, 1 ,4-butanediol monovinyl ether, 1 ,4-butanediol divinyl ether, ethylene glycol monovinyl ether, ethylene glycol divinyl ether, propylene glycol monovinyl ether, propylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, vinyl glycidyl ether, allyl phenyl ether, allyl ethyl ether, diallyl ether, vinyl allyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1 ,4-butanediol monoallyl ether, 1 ,4-butanediol diallyl ether, ethylene glycol monoallyl ether, ethylene glycol diallyl ether, propylene glycol monoallyl ether, propylene glycol diallyl ether, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, polypropylene glycol monoallyl ether, polypropylene glycol diallyl ether, and allyl glycidyl ether; maleimide compounds, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; acrolein and methacrolein; cyclopolymerizable compounds, such as 1 ,6-heptadiene and diallylammonium salts; and N-vinyl pyrrolidone, N- vinyl carbazole; preferred are styrene, a-methylstyrene, vinyl chloride, vinylidene chloride, methacrylate esters, acrylate esters, methacrylonitrile, acrylonitrile, vinyl acetate, and maleimide compounds, more preferred are methacrylate esters and acrylate esters, and most preferred are methyl methacrylate, n-butyl acrylate, or a combination of these.
4. The method according to any one of claims 1 to 3, wherein the monomer carrying functional groups comprises at least one monomer having the formula (II):
Figure imgf000030_0001
wherein R1 is H or methyl and R2 represents or contains a crosslinkable functional group.
5. The method according to claim 4, wherein the crosslinkable functional group includes one or more of crosslinkable silyl, carboxyl, epoxy, hydroxyl and acrylamide groups, provided that when the vinyl monomer contains hydroxyl, the crosslinkable functional group is not hydroxyl.
6. The method according to claim 5, wherein the crosslinkable functional group includes one or more of carboxyl, epoxy, hydroxyl and acrylamide groups, and the method further comprises (c) removing the RAFT end groups by aminolysis.
7. The method according to claim 5, wherein the crosslinkable functional group includes silyl, and the method further comprises (c1) removing the RAFT end groups by aminolysis in the presence of a silane group-containing compound represented by general formula (III):
X1
R4— S Ii — .1
X1 (H wherein R4 is C8-Ci6-alkyl, vinyl group, or C2-Ci0-alkyl, prerferably C3-C8-alkyl, more prerferably C3-C6-alkyl, substituted or interupted by one or more amine groups, prerferably one, two or three amine groups, more prerferably one or two amine groups, and each X1 is independently of one another -OCH3, -OCH2CH3 or -OCH2CH2CH3.
8. The method according to claim 7, wherein the monomer carrying silyl groups is at least one compound selected from the group consisting of a compound represented by general formula (H-1):
Figure imgf000031_0001
wherein R3 is H or methyl, Z1 is Ci-C4-alkylene, preferably propylene, each X is independently of one another -OCH3, -OCH2CH3 or -OCH2CH2CH3, and Y is H, -CH3, -OCH3, -OCH2CH3 or - OCH2CH2CH3.
9. The method according to any one of claims 6 to 8, wherein the thiocarbonylthio group- containing compound is allowed to react with amine compounds, which include hydroxylamine sulfate, hydroxylamine, N-(2-aminoethyl)ethanolamine, N-methylethanolamine, 12- aminododecanoic acid, 3-amino-1-propanol, amine-modified acrylic polymers, allylamine, diallylamine, isopropylamine, diisopropylamine, 3,3'-iminobis(propylamine), ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, 3-(2-ethylhexyloxy)propylamine, 3- ethoxypropylamine, diisobutylamine, 3-(diethylamino)propylamine, di-2-ethylhexylamine, 3- (dibutylamino)propylamine, tert-butylamine, sec-butylamine, n-butylamine, n-propylamine, isopropylamine, 3-(methylamino)propylamine, 3-(dimethylamino)propylamine, N-methyl-3,3'- iminobis(propylamine), 3-methoxypropylamine, isopropanolamine, N-isopropylacrylamide, iminodiacetic acid, 3,3'-iminodipropionitrile, monoethanolamine, diethanolamine, N- ethylethylenediamine, ethyleneimine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-carboxy-4,4'-methylenebiscyclohexylamine, carbohydrazides, guanidine hydrochloride, guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate, aminoguanidine hydrochloride, aminoguanidine bicarbonate, guanylthiourea, guanylurea phosphate, guanylurea sulfate, glycylglycine, 2-chloroethylamine, 1 ,4-diaminobutane, 1 ,2-diaminopropane, 1 ,3-diaminopropane, diaminomaleonitrile, cyclohexylamine, cyclopentylamine, dicyandiamide, dicyclohexylamine, N-(3- (dimethylamino)propyl)acrylamide, N-(3-(dimethylamino)propyl)methacrylamide, dimethylamineborane, dimethylhydrazine, N,N'-ethylenebis(stearoamide), amide oleate, amide stearate, N,N'-methylenebis(stearoamide), methylol stearoamide, 3,9-bis(3-aminopropyl)- 2,4,8, 10-tetraoxaspiro[5,5]undecane, CTU guanamine, thiocarbohydrazide, thiosemicarbazide, thiourea, dihydrazide dodecanedioate, trans-1 ,2-cyclohexanediamine, dihydrazide adipate, dihydrazide sebacate, dihydrazide isophthalate, thiourea dioxide, 2- hydroxyethylaminopropylamine, isobutylamine, 2-bromoethylamine, hexamethylenediamine, 1 ,6-hexamethylenebis(N,N-dimethylsemicarbazide), n-hexylamine, polyethyleneimine, formamidine, formamidine acetate, formamide, methacrylamide, ammonia, monomethylamine, dimethylamine, trimethylamine, N,N'-methylenebis(acrylamide), N-methylolacrylamide, monomethylhydrazine, 3-(lauryloxy)propylamine, acetanilide, acetoacet-o-anisidide, acetoacetanilide, acetoacet-m-xylidide, acetoacet-o-chloroanilide, acetoacet-2,5,- dimethoxyanilide, acetoacet-2,5-dimethoxy-4-chloroanilide, acetoacet-o-toluidide, acetoacet-p- toluidide, o-anisidine, p-anisidine, aniline, p-aminoacetanilide, p-aminobenzoic acid, ethyl p- aminobenzoate ester, 2-amino-4-chlorophenol, 2-aminothiazole, 2-aminothiophenol, 2-amino-5- nitrobenzonitrile, o-aminophenol, m-aminophenol, p-aminophenol, p-aminobenzaldehyde, 4- 31 aminobenzonitrile, anthranilic acid, 3-isopropoxyaniline, N-ethylaniline, N-ethylene toluene sulfonamide, 2,4-xylidine, 3,4-xylidine, m-xylylenediamine, p-cresidine, dianisidine, 4,4<1> - diaminostilbene-2,2'-disulfonic acid, 1 ,4-diaminoanthraquinone, 4,4'-diamino-3,3'- diethyldiphenylmethane, 4,4'-diaminobenzanilide, N,N-diethylaniline, diaminodiphenyl ether, diaminonaphthalene, diaminoanthracene, diphenylamine, dibenzylamine, N,N-dimethylaniline, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, sulfanilic acid, 1 , 1 , 1 ', 1 '-tetramethyl-4,4'- (methylenedi-p-phenylene)disemicarbazide, tobias acid, 2,4,5-trichloroaniline, o-tolidine, o- toluidine, m-toluidine, p-toluidine, m-toluylenediamine, sodium naphthionate, o-nitroaniline, m- nitroaniline, p-nitroaniline, o-nitro-p-chloroaniline, m-nitro-p-toluidine, o-chloro-p-toluidine-m- sulfonic acid, p-hydroxyphenylacetamide, 7-anilino-4-hydroxy-2-naphthalenesulfonic acid, phenylhydrazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, p- phenetidine, phenethylamine, benzylamine, benzophenone hydrazone, mesidine, metanilic acid, N-methylaniline, 2-methyl-4-nitroaniline, 2-methyl-4-methoxydiphenylamine, 2-amino-5- methylbenzenesulfonic acid, leuco-1 ,4-diaminoanthraquinone, paramine, p- hydroxyphenylglycine, acetaldehyde ammonia, acetoguanamine, 3-amino-1 , 2, 4-triazole, 2- aminopyridine, 3-aminopyridine, 4-aminopyridine, 1-(2-aminoethyl)piperazine, N-(3- aminopropyl)morpholine, 1-amino-4-methylpiperazine, isocyanuric acid, imidazole, 2- methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2- heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1- (cyanoethylaminoethyl)-2-methylimidazole, N-(2-(2-methyl-1-imidazolyl)ethyl)urea, 2,4-diamino- 6-(2-methyl-1-imidazolylethyl)-1 ,3,5-triazine, 2,4-diamino-6-(2-undecyl-1-imidazolylethyl)-1 ,3,5- tiazine, 2,4-diamino-6-(2-ethyl-4-methyl-1-imidazolylethyl)-1 ,3,5-tiazine, 2-phenyl-4-methyl-5- hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, an adduct of 2- methylimidazole and isocyanuric acid, an adduct of 2-phenylimidazole and isocyanuric acid, an adduct of 2,4-diamino-6-(2-methyl-1-imidazolylethyl)-1 ,3,5-triazine and isocyanuric acid, 2- methyl-4-formylimidazole, 2-phenyl-4-formylimidazole, 4-formylimidazole, 2,4-dimethyl-5- formylimidazole, 2,4-diphenyl-5-formylimidazole, 4-methylimidazole, 4-methyl-5- (hydroxymethyl)imidazole, 2-amino-4,5-dicyanoimdazole, imidazole-4,5-dicarboxylic acid, 3- carbamoyl-2-pyrazine carboxylic acid, imide succinate, quinaldine, quinoline, 1 ,3-di(4- piperidyl)propane, 2-imidazolidinone, 5,5-dimethylhydantoin, 2,5-dimethylpiperazine, cis-2,6- dimethylpiperazine, 3,5-dimethylpyrazole, 2-methyl-4-pyrazolone, 5,5'-bi-1 H-tetrazole, 5-phenyl- 1 H-tetrazole, 5-methyl-IH-tetrazole, 1 ,2,3,4-tetrahydroquinoline, bis(aminopropyl)piperazine, 1 ,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, hydantoin, (hydroxyethyl)piperazine, 2- pipecoline, 3-pipecoline, 4-pipecoline, 2-(1-piperazinyl)pyrimidine, piperazine, piperidine, pyrrolidine, pyrrole, phenylpyrazolidone, benzoguanamine, N-methylpiperazine, 2- methylpiperazine, 3-methyl-5-pyrazolone, 1-methylol-5,5-dimethylhydantoin, melamine, and morpholine.
10. The method according to any one of claims 1 to 9, wherein the polymerization initiator includes peroxide polymerization initiators, such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1 ,1 ,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butyl-a-cumyl peroxide, di-a-cumyl peroxide, 1 ,4-bis[(tert-butylperoxy)isopropyl]benzene, 1 ,3-bis[(tert- 32 butylperoxy)isopropyl]benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5- bis(tert-butylperoxy)-3-hexyne, 1 ,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4- bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, tert-butylperoxy acetate, tertbutylperoxy isobutylate, tert-butylperoxy octoate, tert-butylperoxy pivalate, tert-butylperoxy neodecanoate, tert-butylperoxy-3,5,5-trimethyl hexanoate, tert-butylperoxy benzoate, tert- butylperoxy laurate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, bis(2-ethylhexyl)peroxy dicarbonate, diisopropylperoxy dicarbonate, di-sec-butylperoxy dicarbonate, di-n-propylperoxy dicarbonate, bis(3-methoxybutyl) peroxy dicarbonate, bis(2-ethoxyethyl)peroxy dicarbonate, bis(4-tert-butylcyclohexyl)peroxy dicarbonate, O-tert-butyl-O-isopropylperoxy carbonate, and succinic acid peroxide; azo polymerization initiators, such as 2,2'-azobis-(2- amidinopropane)dihydrochloride, 2,2'-azobis(dimethylisobutyrate), 2,2'-azobis-(4-methoxy-2,4- dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 1 ,1'-azobis(cyclohexane-1 -carbonitrile), azocumene, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis-(2,4-dimethylvaleronitrile, 4,4'- azobis(4-cyanovaleric acid), 2-(tert-butylazo)-2-cyanopropane, 2,2'-azobis(2,4,4- trimethylpentane), and 2,2'-azobis(2-methylpropane); inorganic peroxides, such as potassium persulfate and sodium persulfate; vinyl monomers which thermally generate radical species, such as styrene; compounds which generate radical species by light, such as benzoin derivatives, benzophenone, acylphosphine oxide, and photo-redox systems; and redox polymerization initiators including sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, or the like, as a reducing agent, and potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, or the like, as an oxidizing agent.
11. A terminal-functional polymer, especially a silyl-terminated polymer obtained by the method according to any one of claims 1 to 10.
12. The polymer according to claim 11 , which has a number-average molecular weight (Mn) of 10,000 to 1 ,000,000, preferably 20,000 to 500,000, and more preferably 30,000 to 200,000.
13. The polymer according to claim 11 or 12, which has a ratio (Mw/Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of 3.0 or less, preferably 2.0 or less, more preferably 1 .5 or less.
14. The polymer according to any one of claims 11 to 13, which has a degree of polymerization for monomer carrying functional groups of 1 .0 to 5, preferably 1 .2 to 4.
15. A sealant or adhesive composition, comprising the polymer according to any one of claims 11 to 14.
16. The sealant or adhesive composition according to claim 15, further comprising catalysts and/or one or more additives.
17. The sealant or adhesive composition according to claim 16, wherein the catalysts include titanate esters, such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds, such as dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; lead compounds, such as lead octylate; amine compounds, such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, 33 cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N- methylmorpholine, and 1 ,3-diazabicyclo[5.4.6]undecene-7; carboxylate salts of these amine compounds; alkaline catalyst, such as potassium hydroxide, sodium hydroxide, sodium and potassium methylate; acid or acid salt such as a lower alkyl carboxylic acid (e.g. C2 to C6 carboxylic acid), such as acetic acid, valeric acid; a poly-carboxylic acid such as citric acid, malic acid, maleic acid, succinic acid, malonic acid, hippuric acid, tartaric acid, oxalic acid; a medi- um/long chain acid such as lauric acid, stearic acid; phosphoric acids such as phenyl phosphoric acids; any other acid such as levulinic acid, benzoic acid, boric acid, trifluoroacetic acid; or- ganic bismuth compound, such as bismuth carboxylate, especially bismuth octoate, bismuth ethylhexanoate, bismuth neodecanoate or bismuth pivalate.
18. The sealant or adhesive composition according to claim 16 or 17, wherein the additives include one or more selected from the group consisting of ultraviolet (UV) light absorbers, fillers, lightweight fillers, thixotropy agents, plasticizers, adhesion promoters, anti-aging agents, dehy- drating agents, flame retardants, vulcanization promoters and whitening agent or colorant.
19. Use of the polymer according to any one of claims 11 to 14 for sealant or adhesive application.
PCT/EP2021/082551 2020-12-02 2021-11-22 Method for producing a terminal-functional polymer WO2022117389A1 (en)

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