WO2010108939A1 - Vinyl ester resin composition - Google Patents
Vinyl ester resin composition Download PDFInfo
- Publication number
- WO2010108939A1 WO2010108939A1 PCT/EP2010/053808 EP2010053808W WO2010108939A1 WO 2010108939 A1 WO2010108939 A1 WO 2010108939A1 EP 2010053808 W EP2010053808 W EP 2010053808W WO 2010108939 A1 WO2010108939 A1 WO 2010108939A1
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- WIPO (PCT)
- Prior art keywords
- resin composition
- composition according
- meth
- acrylate
- resin
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
Definitions
- the present invention relates to a resin composition
- a resin composition comprising (a) from 30 to 70 wt.% of a vinyl ester resin and (b) from 30 to 70 wt.% of reactive diluent.
- a resin composition containing methacrylate containing compound as reactive diluent is for example described in WO-A-2008/077586.
- WO-A-2008/077586 describes that such resin compositions can suitable be applied in relining.
- the viscosity of the resin composition is not too high.
- relining encompasses impregnating of fiber with resin composition. Therefore, viscosity of the resin composition may not be too high in view of handling and time for impregnation.
- the object of the present invention is obtaining a resin composition with a reduced viscosity, while mechanical properties of the cured objects are retained or even more improved, as indicated by for example tensile strength, tensile modulus, flexural strength and/or flexural modulus.
- the resin composition according to the invention comprises methacrylate containing compound and an ester of itaconic acid as reactive diluent.
- An additional surprising advantage is that the elongation at break of the cured object may also be improved.
- the composition according to the invention comprises from 30 to 70 wt.% of at least one vinyl ester resin As used herein, all amounts in wt.% are given relative to the total weight of the vinyl ester resin(s) (a) and reactive diluents (b), unless otherwise specified.
- the vinyl ester resin as is comprised in the vinyl ester resin composition according to the invention may suitably be selected from the vinyl ester resins as are known to the skilled man. Vinyl ester resins are mostly used because of their hydrolytic resistance and excellent mechanical properties. Vinyl ester resins having unsaturated sites only in the terminal position are for example prepared by reaction of epoxy oligomers or polymers (e.g.
- a vinyl ester resin is an oligomer or polymer containing at least one (meth)acrylate functional end group, also known as (meth)acrylate functional resins. This also includes the class of vinyl ester urethane resins (also referred to as urethane (meth)acrylate resins).
- Preferred vinyl ester resins are methacrylate functional resins including urethane methacrylate resins and resins obtained by reaction of an epoxy oligomer or polymer with methacrylic acid or methacrylamide, preferably with methacrylic acid. Most preferred vinyl ester resins are resins obtained by reaction of an epoxy oligomer or polymer with methacrylic acid.
- the vinyl ester resin as is comprised in the vinyl ester resin composition according to the invention preferably has a molecular weight Mn in the range from 500 to 3000 Dalton, more preferably in the range from 500 to 1500.
- Mn molecular weight
- the molecular weight of the vinyl ester resin is determined in tetrahydrofurane using gel permeation chromatography according to ISO 13885-1 employing polystyrene standards and appropriate columns designed for the determination of the molecular weights.
- the vinyl ester resin preferably has an acid value in the range from 0 to 50 mg KOH/g resin and more preferably in the range from 0 to 30 mg KOH/g resin.
- the acid value of the vinyl ester resin is determined titrimetrically according to ISO 2114-2000.
- the vinyl ester resin composition according to the invention comprises at least one methacrylate reactive diluent.
- the resin composition comprises a methacrylate functional resin as vinyl ester resin
- the resin composition according to the invention comprises, as reactive diluent, a methacrylate containing compound different from the methacrylate functional resin.
- a methacrylate reactive diluent is a diluent comprising at least one reactive methacrylate group.
- methacrylate reactive diluents are monofunctional and difunctional methacrylates.
- the resin composition according to the invention comprises a reactive diluent.
- the diluent will be applied , for instance, for lowering of the viscosity of the resin composition in order to make handling thereof more easy.
- a reactive diluent is a diluent that is able to copolymerize with the vinyl ester resin present in the composition according to the invention.
- at least 25 wt. % of the methacrylate reactive diluent is a difunctional methacrylate diluent having a molecular weight M n in the range from 200 to 500.
- Suitable examples of difunctional reactive diluents having a molecular weight M n in the range from 200 to 500 are PEG200 di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 1 ,3-butanediol di(meth)acrylate, 2,3-butanedioldi(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate and its isomers, diethyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentyl glycol di(meth)acrylate, dipropyleneglycol di(meth)acrylate, tripropyleneglycol di(meth)acrylate, PPG250 di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate
- the difunctional methacrylate diluent is selected from 1 ,4-butanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, PEG200 di(meth)acrylate, triethylene glycol di(meth)acrylate and/or tripropylene glycol di(meth)acrylate.
- the resin composition may further comprise a monofunctional methacrylate preferably selected from tetrahydro furfuryl (meth)acrylate, hydroxyl ethyl (meth)acrylate and/or hydroxyl propyl (meth)acrylate.
- the resin composition may further comprise another ethylenically unsaturated reactive diluent, for example styrene, ⁇ -methylstyrene, N-vinylpyrrolidone and N-vinylcaprolactam.
- the resin composition contains less than 2 wt.% styrene, preferably the resin composition is essentially styrene-free.
- a low amount of styrene is advantageous as styrene may escape during the preparation and curing, or even during the envisaged long-term use thereof, and causes an undesirable odour, and possibly even also toxic effects.
- the resin composition preferably further comprises a co-initiator for the radical curing of the resin composition, in an amount of 0.00001 to 10wt% .
- a preferred co- initiator is an amine or a transition metal compound.
- the amine co-initiator that may be present in the composition is preferably an aromatic amine and even more preferably a tertiary aromatic amine.
- Suitable accelerators include N,N-dimethylaniline, N,N-diethylaniline; toluidines and xylidines such as N,N-diisopropanol-para-toluidine; N,N-dimethyl-p-toluidine; N,N-bis(2-hydroxyethyl)xylidine and -toluidine.
- the amount of amine in the resin composition is generally at least 0.00001 wt.% and preferably at least 0.01 wt.% and more preferably at least 0.1 wt.%. Generally, the amount of amine in the resin composition is at most 10 wt.%, preferably at most 5 wt.%. - A -
- transition metal compounds as co-initiator are compounds of a transition metal with an atomic number of in the range from 22 to 29 or with an atomic number in the range from 38 to 49 or with an atomic number in the range from 57 to 79, such as vanadium, iron, manganese, copper, nickel, molybdenum, tungsten, cobalt, chromium compounds.
- Preferred transition metals are V, Cu, Co, Mn and Fe.
- the resin composition preferably further comprises one or more radical inhibitors, preferably chosen from the group of phenolic compounds, benzoquinones, hydroquinones, catechols, stable radicals and/or phenothiazines.
- radical inhibitors preferably chosen from the group of phenolic compounds, benzoquinones, hydroquinones, catechols, stable radicals and/or phenothiazines.
- the amount of radical inhibitor as used in the context of the present invention may, however, vary within rather wide ranges, and may be chosen as a first indication of the gel time as is desired to be achieved.
- radical inhibitors that can be used in the resin compositions according to the invention are, for instance, 2-methoxyphenol, 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-trimethyl-phenol, 2,4,6-tris-dimethylaminomethyl phenol, 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-isopropylidene diphenol, 2,4-di-t-butylphenol, 6,6'-di-t-butyl-2,2'-methylene di-p-cresol, hydroquinone, 2-methylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,6-di-t-butylhydroquinone, 2,6-dimethylhydroquinone , 2,3,5-trimethylhydroquinone, catechol, 4-t
- the amount of radical inhibitor in the resin composition according to the invention is in the range of from 0,0001 to 10 % by weight. More preferably, the amount of inhibitor in the resin composition is in the range of from 0,001 to 1 % by weight. The skilled man quite easily can assess, in dependence of the type of inhibitor selected, which amount thereof leads to good results according to the invention.
- the resin composition according to the invention comprises an ester of itaconic acid as reactive diluent (herein after referred to as itaconate ester), preferably in an amount of from 5 to 50 wt.%.
- the itaconate ester is preferably selected from mono(cyclo)alkyl itaconates, di-(cyclo)alkyl itaconates, diol di-itaconates and triol tri-itaconates.
- Preferred mono(cyclo)alkyl itaconates are C5-C8 cycloalkyl itaconate and C1-C12 alkyl itaconates, more preferably C1-C6 alkyl itaconates.
- Preferred di-(cyclo)alkyl itaconates are di-C5-C8 cycloalkyl itaconate, di-C1-C12 alkyl itaconates, more preferably di- C1- C6 alkyl itaconates.
- alkyl itaconates are methyl itaconate, ethyl itaconate, propyl itaconate, isopropyl itaconate, hydroxyethyl itaconate.
- a preferred example of a cycloalkyl itaconate is cyclohexyl itaconate.
- di-alkyl itaconates are dimethyl itaconate, diethyl itaconate, dipropyl itaconate, di-isopropyl itaconate, di-hydroxyethyl itaconate dihexyl itaconate.
- a preferred example of a di-cycloalkyl itaconate is di-cyclohexyl itaconate.
- diol di-itaconates are for instance butanediol di-itaconate, butanediol di-itaconate dimethyl ester, (poly)ethyleneglycol di-itaconate, (poly)ethyleneglycol di-itaconate diethylester , (poly)propyleneglycol di-itaconate, (poly)propyleneglycol di-itaconate diethylester
- triol tri-itaconates are for instance trimethylolpropane tri-itaconate, trimethylolpropane. tri-itaconate trimethyl ester and ethoxylated and propoxylated versions thereof.
- the composition according to the present invention comprises a diester of itaconic acid as itaconate ester.
- a diester of itaconic acid is used as itaconate ester
- the diester of itaconic acid preferably has formula
- a and B may be different or the same and A and/or B being an alkyl group having from 1 to 12 carbon atoms, more preferably from 1 to 6 carbon atoms.
- dimethylitaconate is used as reactive diluent.
- the composition preferably comprises itaconate ester(s) in an amount, relative to the total amount of reactive diluent, of from 5 to 95 wt.%, preferably from 15 to 85 wt.% and more preferably from 20 to 80 wt.%.
- the itaconate esters are derived from a non fossil source, such as for example corn.
- the weight ratio of methacrylate containing compound (excluding vinyl ester resin) and itaconate esters is preferably in the range of from 10:1 to 1 :10, more preferably from 5:1 to 1 :5 and even more preferably from 4:1 to 1 :4. because within these ratios the advantageous effects of the invention become even more pronounced.
- the present invention further relates to a process for radically curing the resin composition according to the invention, wherein the curing is effected by adding an initiator to the resin composition as described above.
- the curing is effected at a temperature in the range of from -20 to +200 0 C, preferably in the range of from -20 to +100 0 C, and most preferably in the range of from -10 to +60 0 C (so-called cold curing).
- the initiator is a photoinitiator, a thermal initiator and/or redox initiator.
- a photo initiator is capable of initiating curing upon irradiation
- Photo initiation is understood to be curing using irradiation with light of a suitable wavelength (photo irradiation). This is also referred to as light cure.
- a photo-initiating system may consist of a photo initiator as such, or may be a combination of a photo initiator and a sensitizer, or may be a mixture of photo initiators, optionally in combination with one or more sensitizers.
- the photo initiating system that can be used in the context of the present invention can be chosen from the large group of photo-initiating systems known to the skilled person.
- a vast number of suitable photo initiating systems can be found in, for instance, Volume 3 of "Chemistry and Technology of UV and EB Formulations", 2 nd Edition, by K. Dietliker and J. V. Crivello (SITA Technology, London; 1998).
- the thermal initiator can be selected from azo compounds like for example azo isobutyronitril (AIBN), C-C labile compounds like for example benzopinacole, peroxides, and mixtures thereof .
- the thermal initiator is preferably an organic peroxide, or a combination of two or more organic peroxides.
- the redox initiator is preferably an organic peroxide in combination with at least one of the above mentioned co-initiators.
- suitable peroxides are, for instance, hydroperoxides, peroxy carbonates (of the formula -OC(O)OO-), peroxyesters (of the formula -C(O)OO-), diacylperoxides (of the formula -C(O)OOC(O)-), dialkylperoxides (of the formula -00-), etc.
- the present invention further also relates to objects and structural parts prepared from such vinyl ester resin compositions by curing with an initiator as described above.
- structural resin compositions are capable of providing structural parts.
- such resin compositions are non-aqueous systems. They contain at most 5% by weight of water, mainly resulting from the reactions during resin preparation.
- structural parts are considered to have a thickness of at least 0.5 mm and appropriate mechanical properties. End segments where the resin compositions according to the present invention can be applied are for example automotive parts, boats, chemical anchoring, roofing, construction, containers, relining, pipes, tanks, flooring, windmill blades.
- Resin formulations were prepared using 55Og Atlac 5808 (commercially available from DSM Composite Resins B.V.), x g Butanediol dimethacrylate, y g polyethylene glycol dimethacrylate, z g dimethylitaconate and 3Og cobalt solution (NL-49P). See Table 1.
- Curing was monitored by means of standard gel time equipment. This is intended to mean that both the gel time (T ge ⁇ or T 2 5->35°c) and peak time (T p ⁇ ak or T 2 5-> P ea k ) were determined by exotherm measurements according to the method of DIN 16945 when curing the resin with the peroxide as indicated. Table 1
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10709845.1A EP2411470B1 (en) | 2009-03-25 | 2010-03-24 | Vinyl ester resin composition |
BRPI1011705A BRPI1011705A8 (en) | 2009-03-25 | 2010-03-24 | VINYL ESTER RESIN COMPOSITION |
US13/255,917 US8598293B2 (en) | 2009-03-25 | 2010-03-24 | Vinyl ester resin composition |
DK10709845.1T DK2411470T3 (en) | 2009-03-25 | 2010-03-24 | VINYL ESTER RESIN COMPOSITION |
JP2012501291A JP5598934B2 (en) | 2009-03-25 | 2010-03-24 | Vinyl ester resin composition |
CN201080013576.1A CN102361933B (en) | 2009-03-25 | 2010-03-24 | Vinyl ester resin composition |
ES10709845.1T ES2498722T3 (en) | 2009-03-25 | 2010-03-24 | Composition of vinyl ester resin |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09156128.2 | 2009-03-25 | ||
EP09156128 | 2009-03-25 |
Publications (1)
Publication Number | Publication Date |
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WO2010108939A1 true WO2010108939A1 (en) | 2010-09-30 |
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ID=40527593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2010/053808 WO2010108939A1 (en) | 2009-03-25 | 2010-03-24 | Vinyl ester resin composition |
Country Status (8)
Country | Link |
---|---|
US (1) | US8598293B2 (en) |
EP (1) | EP2411470B1 (en) |
JP (1) | JP5598934B2 (en) |
CN (1) | CN102361933B (en) |
BR (1) | BRPI1011705A8 (en) |
DK (1) | DK2411470T3 (en) |
ES (1) | ES2498722T3 (en) |
WO (1) | WO2010108939A1 (en) |
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Also Published As
Publication number | Publication date |
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CN102361933A (en) | 2012-02-22 |
US8598293B2 (en) | 2013-12-03 |
US20120116025A1 (en) | 2012-05-10 |
BRPI1011705A2 (en) | 2016-03-22 |
BRPI1011705A8 (en) | 2017-10-03 |
EP2411470B1 (en) | 2014-06-04 |
DK2411470T3 (en) | 2014-09-08 |
EP2411470A1 (en) | 2012-02-01 |
JP2012521464A (en) | 2012-09-13 |
JP5598934B2 (en) | 2014-10-01 |
CN102361933B (en) | 2014-02-12 |
ES2498722T3 (en) | 2014-09-25 |
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