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Title:
UNSATURATED POLYESTER RESIN COMPOSITION
Document Type and Number:
WIPO Patent Application WO/2012/130971
Kind Code:
A1
Abstract:
This invention relates to an unsaturated polyester resin composition comprising an unsaturated polyester (a), a monomer (b) copolymerizable with said unsaturated polyester and a tertiary aromatic amine (c), characterized in that the composition comprises an unsaturated polyester (a1) comprising building blocks according to formula (1) and a monomer (b1) according to formula (2) whereby n= 0-3; R1 and R2 each individually represent H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl or C7-C20 arylalkyl; X = O, S or NR3 whereby R3 = H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, part of a polymer chain or attached to a polymer chain.

Inventors:
HILKER IRIS (DE)
JANSEN JOHAN FRANZ GRADUS ANTONIUS (NL)
Application Number:
PCT/EP2012/055679
Publication Date:
October 04, 2012
Filing Date:
March 29, 2012
Export Citation:
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Assignee:
DSM IP ASSETS BV (NL)
HILKER IRIS (DE)
JANSEN JOHAN FRANZ GRADUS ANTONIUS (NL)
International Classes:
C08F283/01; C08K5/01; C08K5/098; C08K5/14; C08K5/18; C08K13/02; C09D167/00
Domestic Patent References:
WO1997044399A11997-11-27
Foreign References:
GB1137903A1968-12-27
US20030130414A12003-07-10
Other References:
FRANCK, ADOLF: "Kunststoff-Kompendium", 2000, VOGEL BUCHVERLAG, Würzburg, ISBN: 3-8023-1855-2, article ADOLF F. ET AL: "8.4.2: Vernetzte Polyester", pages: 382 - 386, XP002657022
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 21 May 2009 (2009-05-21), KAWADA ET AL: "Curable compositions and their cured products with good heat and scratch resistance, high transparency, and hardness", XP002656932, retrieved from STN Database accession no. 2009:615549
R. A. T. M. VAN BENTHEM; L. J. EVERS; J. MATTHEIJ; A. HOFLAND; L. J. MOLHOEK; A. J. DE KONING; J. F. G. A. JANSEN; M. VAN DUIN: "Handbook of Polymer Reaction Engineering", pages: 869 - 871
"Chemical & Engineering News", vol. 89, pages: 11
GARY M. KSANDER; JOHN E. MCMURRY; MARK JOHNSON: "A Method for the Synthesis of Unsaturated Carbonyl Compounds", J. ORG. CHEM., vol. 42, no. 7, 1977, pages 1180 - 1185, XP002130735, DOI: doi:10.1021/jo00427a017
MITSURU UEDA; MASAMI TAKAHASI: "Radical-Initiated Homo- and Copolymerization of a-Methylene-y-Butyrolactone", J. POL. SCI. A, vol. 20, 1982, pages 2819 - 2828
Attorney, Agent or Firm:
VERHAEGEN, Ilse (AA Echt, NL)
Download PDF:
Claims:
CLAIMS

Unsaturated polyester resin composition comprising an unsaturated polyester (a), a monomer (b) copolymerizable with said unsaturated polyester, and a tertiary aromatic amine (c), characterized in that the composition comprises an unsaturated polyester (a1) comprising building blocks according to formula (1) o ιΛΛΛΛΛΛΛ Ov

O ΛΛΛΑΛΛΛ

(1)

and a monomer (b1) according to formula (2)

whereby n= 0-3; Ri and R2 each individually represent H, Ci-C2o alkyl, C3-C2o cycloalkyl, C6-C2o aryl, C7-C20 alkylaryl or C7-C20 arylalkyl; X = O, S or NR3 whereby R3 = H, C C2o alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, part of a polymer chain or attached to a polymer chain.

Unsaturated polyester resin composition according to claim 1 , characterized in that compound (b1) is according to formula (3).

whereby Ri is H or CH3.

Unsaturated polyester resin composition according to anyone of the preceding claims, characterized in that the the unsaturated polyester (a1) comprising building blocks according to formula (1) has an acid value in the range of from 40 to 150 m KOH/g of resin, preferably in the range of from 45 to 100 mg KOH/g of resin.

Unsaturated polyester resin composition according to anyone of the preceding claims, characterized in that the number-average molecular weight Mn of the unsaturated polyester (a1) comprising building blocks according to formula (1) is in the range of from 500 to 10000 g/mol, preferably from 700 to 5000 g/mol and more preferably from 900 to 3000 g/mol.

Unsaturated polyester resin composition according to anyone of the preceding claims, characterized in that the amount of tertiary aromatic amine (c) relative to the total amount of compounds (a) and (b) is from 0.01 to 10 wt.%.

Unsaturated polyester resin composition according to anyone of the preceding claims, characterized in that the resin composition comprises an additional ethylenically unsaturated compound (b2) with a number-average molecular weight Mn of at most 300 g/mol.

Process for radically curing an unsaturated polyester resin composition according to anyone of the preceding claims 1-6, characterized in that the curing is effected with a peranhydride (d).

Process according to claim 7, characterized in that the molar amount of peranhydride (compound (d)) relative to the total amount of compound (a) and compound (b) is from 0.01 to 10 wt.% .

Process according to anyone of the preceding claims 7 or 8, characterized in that the molar amount of peranhydride relative to the molar amount of teriary aromatic amine (compound (c)) is from 0.1 to 10.

Process according to anyone of the preceding claims 7-9, characterized in that the process comprises adding the peranhydride to a composition comprising compounds (a), (b) and (c).

Process according to claim 10, characterized in that said adding is done by mixing the peranhydride into the composition comprising compounds (a), (b) and (c).

Multicomponent system comprising an unsaturated polyester (a1) comprising building blocks according to formula (1)

a monomer (b1) according to formula (2)

whereby n= 0-3; and R2 each individually represent H, C C2o alkyl, C3-C20 cycloalkyl, C6-C2o aryl, C7-C20 alkylaryl or C7-C20 arylalkyl; X = O, S or NR3 whereby R3 = H, C C2o alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7- 20 arylalkyl, part of a polymer chain or attached to a polymer chain, a tertiary aromatic amine (c)

and a peranhydride (d).

Multicomponent system according to claim 12 comprising at least two components, characterized in that the first component is the unsaturated polyester resin composition according to any of the claims 1-6 and the second component comprises a peranhydride.

14. Cured object obtained by curing an unsaturated polyester resin composition according to anyone of claims 1-6 with a peranhydride or obtained by the process according to claim 7-1 1 or obtained by mixing the components of the multicomponent system according to claim 12 or 13.

Use of the cured object of claim 14 in automotive, boats, chemical anchoring, roofing, construction, containers, relining, pipes, tanks, flooring or windmill blades.

Description:
UNSATURATED POLYESTER RESIN COMPOSITION

The present invention relates to an unsaturated polyester resin composition comprising an unsaturated polyester (a), a reactive diluent (b) and a tertiary aromatic amine (c).

The present invention further also relates to objects and structural parts prepared from such unsaturated polyester resin compositions by curing with a peranhydride. The present invention finally also relates to methods of peranhydride curing of unsaturated polyester resin compositions.

As meant herein, objects and structural parts are considered to have a thickness of at least 0,5 mm and appropriate mechanical properties. The term "objects and structural parts" as meant herein also includes cured resin compositions as are used in the field of chemical anchoring, construction, roofing, flooring, windmill blades, containers, tanks, pipes, automotive parts, boats, etc.

Unsaturated polyester resin compositions, especially those comprising styrene as reactive diluent, are well known in the art. For example, in [R. A. T. M. van Benthem, L. J. Evers, J. Mattheij, A. Hofland, L. J. Molhoek, A. J. de Koning, J. F. G. A. Jansen and M. van Duin, "Handbook of Polymer Reaction Engineering", eds. T. Meyer, J. Keurentjes, chapter 16, pages 869-871] unsaturated polyesters in styrene are described and more particularly, it is stated that in general the ethylenically unsaturated carbons in unsaturated polyesters are based on maleic or fumaric building blocks. In this handbook, styrene is used as the reactive diluent.

Although styrene is a very effective reactive diluent, i.e. has a high copolymerization ability and a good cutting power, it has also several drawbacks. For instance, styrene has an undesirable odour. More importantly, styrene is considered to be a potentially carcinogenic substance (see for instance Chemical & Engineering News, vol. 89, no. 25, page 1 1 , eds. W.G. Schulz, S.L. Cai, http://www.cen-online.org) which is even more hindering since styrene is volatile.

Styrene free unsaturated polyester resin compositions are known. For instance, W097/44399 describes a powder coating composition in which the unsaturated polyester could be based on maleic, fumaric, itaconic, citraconic or mesaconic acid building blocks, although only examples using fumaric building blocks are given. Although these compositions are styrene free, they are employed as powder coatings, i.e. they are solids and consequently not suitable for construction purposes. This is exemplified by the fact that for many construction applications the cured objects are obtained by processes such as vacuum infusion, SMC/BMC, vacuum-assisted resin transfer moulding in which processes solids cannot be used but liquid resin compositions are required.

Consequently, there is still a need for unsaturated polyester resin compositions suitable for construction purposes in which styrene can be partially or completely replaced with another reactive diluent while such new resin composition still has a low viscosity (similar or lower compared to the styrene equivalent), and the reactive diluent has a low odour, is less volatile than styrene (i.e. it should have a higher boiling point) and has a good reactivity (similar or faster compared to styrene) with unsaturated polyester.

Therefore, the object of the present invention is to provide a reactive diluent for unsaturated polyester resins with less odour and being less volatile than styrene, with a sufficient copolymerization ability (reactivity) with the unsaturated polyester resin and with a good cutting power in unsaturated polyester resin compositions and which can result in good curing efficiency (as demonstrated by short gel time, short peak time and/or high peak temperature).

This object has surprisingly been achieved in that the composition comprises an unsaturated polyester (a1) comprising building blocks according to formula (1) νΛΛΛΛΛΛ V

and, as monomer copolymerizable with said unsaturated polyester (a1), a monomer (b1) according to formula (2)

whereby n= 0-3; and R 2 each individually represent H, C C 2 o alkyl, C 3 -C 20 cycloalkyl, C 6 -C 2 o aryl, C 7 -C 20 alkylaryl or C 7 -C 20 arylalkyl; X = O, S or NR 3 whereby R 3 = H, C C 2 o alkyl, C 3 -C 20 cycloalkyl, C 6 -C 2 o aryl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, part of a polymer chain or attached to a polymer chain.

It has surprisingly been found that when the resin composition comprises an unsaturated polyester resin comprising building blocks according to formula (1), styrene can be partially or even completely replaced with a compound according to formula (2) while the reactivity of the compound according to formula (2) with the unsaturated polyester resin comprising building blocks according to formula (1) remains on the same level or may even be improved. It also has been surprisingly found that the monomer (b1) has a similar cutting power compared to styrene in compositions comprising unsaturated polyester resins comprising building blocks according to formula (1) thereby enabeling the formulation of very low viscous resins which are very suitable for all kinds of applications in which vacuum infusion is used. It has furthermore surprisingly been found that the resin compositions according to the invention can be efficiently cured with a peranhydride. An additional advantage of a resin composition according to the invention is that, when performing the curing in air, the cure is similar to the cure with styrene and may outperform alternatives like methacrylates. Furthermore an additional advantage of using compounds according to formula (2) is that they can be prepared from biobased raw materials.

Compounds according to formula (2) can be commercially obtained from for example TCI Europe and can be prepared with the method as described for example by Gary M. Ksander, John E. McMurry, and Mark Johnson, "A Method for the Synthesis of Unsaturated Carbonyl Compounds" in J. Org. Chem. 1977, vol. 42, issue 7, pages 1 180-1 185, or by Mitsuru Ueda and Masami Takahasi, "Radical-Initiated Homo- and Copolymerization of a-Methylene-y-Butyrolactone" in J. Pol. Sci. A 1982, vol. 20, p. 2819-2828.

Preferably, n is 1 or 2. More preferably, n is 1 . X is preferably O. Preferably, Ri and R 2 each individually represent H or CH 3 . More preferably, Ri and R 2 are both H or Ri is H and R 2 is CH 3 . In a preferred embodiment of the invention, the composition comprises a compound (b1) according to formula (3)

whereby is H or CH 3 .

The amount of compound (b1) relative to the total amount of unsaturated polyester (compounds (a)) and monomer copolymerizable with (a) (compounds (b)) is preferably at least 1 wt.%, more preferably at least 5 wt.%, even more preferably at least 10 wt.% and even more preferably at least 25 wt.%. The amount of compound (b1) relative to the total amount of compounds (a) and (b) is preferably at most 99 wt.%, more preferably at most 95 wt.%, more preferably at most 90 wt.%, even more preferably at most 70 wt.% and even more preferably at most 65 wt.%. Preferably, the amount of compound (b1) relative to the total amount of compounds (a) and (b) is from 1 to 95 wt.%, and more preferably from 25 to 65 wt.%.

The composition optionally may further comprise another (than compound with formula (2)) ethylenically unsaturated compound (b2) with a number- average molecular weight M n of at most 300 g/mol. Non-limiting examples are hydroxyethylmethacrylate, hydroxypropylmethacrylate, methyl methacrylate, ethyl methacrylate and laurylmethacrylate or mixtures thereof.

Besides these monomers also solvents may be present in the resin composition. In general the composition comprises less than 5% water as solvent.

An unsaturated polyester is an unsaturated polyester comprising unsaturated diacid building blocks and diol building blocks, and is prepared by the polycondensation of at least one diacid and at least one diol and in which a least a part of the diacids is an unsaturated diacid. According to the invention, at least a part of the unsaturated diacid building blocks are building block according to formula (1)

ΛΛΛΛΛΛΛ/ (1) Besides the unsaturated diacid building block according to formula (1) also other unsaturated diacid building blocks may be present such as for instance fumaric, maleic, citraconic and mesaconic building blocks. Besides the unsaturated diacid building blocks also saturated diacid building blocks may be present such as for example succinic, adipic, ortho-phthalic, iso-phthalic, tere-phthalic, cyclohexane dicarboxylic building blocks. In the resin composition according to the invention, the molar amount of building blocks according to formula (1) relative to the total molar amount of diacid building blocks is preferably from 10% to 100% , more preferably from 30% to 95% and even more preferably from 50% to 90%. In the resin composition according to the invention, the molar amount of building blocks according to formula (1) relative to the total molar amount of α,β-unsaturated diacid building blocks is preferably from 40% to 90%. The diol building block can be any type of diol building block. Non limiting examples are for instance ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, ethoxylated bisphenol A, neopentyl glycol, 1 ,3-propane diol, 1 ,4- butane diol, polymeric diols like poly-THF, polyethylene glycol. For controlling the molecular weight it is also possible that mono-ols and mono acids are employed in the synthesis of unsaturated polyesters comprising building blocks according to formula (1). Similarly when branching is required it is also possible that triols or even tetrols and triacids or tetracids are employed in the synthesis of unsaturated polyesters comprising building blocks according to formula (1).

The acid value of the unsaturated polyester comprising building blocks according to formula (1) can vary widely and is in general between 20 and 160 mg KOH/g primary resin. Preferably the unsaturated polyester comprising building blocks according to formula (1) has an acid value in the range of from 40 to 150 mg KOH/g of resin , more preferably in the range from 45 to 100 mg KOH/g of resin. As used herein, the acid value of the resin is determined titrimetrically according to ISO 21 14-2000.

Preferably the number-average molecular weight M n of the unsaturated polyester comprising building blocks according to formula (1) is in the range of from 500 to 10000 g/mol, preferably from 700 to 5000 g/mol and more preferably from 900 to 3000 g/mol. As used herein, the number-average molecular weight M n of the unsaturated polyester is determined using gel permeation

chromatography according to ISO 13885-1 using polystyrene standards.

The total amount of unsaturated polyester (compound (a)) relative to the total amount of unsaturated polyester (compounds (a)) and monomer copolymerizable with (a) (compounds (b)) is preferably from 20 to 80 wt.%, more preferably from 25 to 75 wt.%, even more preferably from 30 to 70 wt.% and most preferably from 35 to 65 wt.%.

For clarity purposes the term primary resin is introduced. With primary resin or primary resin system is meant the mixture of unsaturated polyester comprising building blocks according to formula (1) (a1), the monomers (b1) according to formula (2) and, in case present, other unsaturated polyester resins and vinyl ester resins (a2) and other ethylenically unsaturated compounds (b2) with a number-average molecular weight M n of at most 300 g/mol.

Preferably the tertiary aromatic amine has the following structure:

in which R4=H, C1-C5 alkyl, 0(C1-C5)alkyl; R5 and R6 are independently selected from C1-C4 alkyl optionally substituted with hydroxyl or (poly) ether groups. Preferably, R4= H or CH3. Preferably R5 and/or R6 are CH3, C2H5, C2H40H, C3H7 and

CH2CH(OH)CH3.

Very suitable examples of tertiary aromatic amines are, for instance,

4-methoxy-N,N-dimethylaniline (R4=OCH3, R5 and R6=CH3), N,N-dimethylaniline (R4=H, R5 and R6=CH3), Ν,Ν-diethylaniline (R4=H, R5 and R6=C2H5), N,N- diethanolaniline (R4=H, R5 and R6=CH2CH20H), N-methyl N-ethanol aniline (R4=H, R5=CH3, R6=CH2CH20H), N,N-diethanoltoluidine(R4=CH3, R5 and

R6=CH2CH20H), Ν,Ν-diethanolaniline mono-methylether (R4=H, R5=CH2CH20H, R6=CH2CH20CH3), Ν,Ν-diethanolaniline dimethylether (R4=H,

R5,R6=CH2CH20CH3), Ν,Ν-diisopropanolaniline (R4=H, R5 and

R6=CH2CH(OH)CH3), Ν,Ν-dimethyltoluidine (R4, R5 and R6 = CH3), N,N- diethyltoluidine (R4=CH3, R5 and R6=C2H5), Ν,Ν-diisopropanoltoluidine DIPT

(R4=CH3, R5 and R6=CH2CH(OH)CH3), Ν,Ν-diisopropanoltoluidine monomethyl ether (R4=CH3, R5=CH2CH(OCH3)CH3, R6=CH2CH(OH)CH3), N,N-diisopropanoltoluidine dimethyl ether((R4=CH3, R5 and R6=CH2CH(OCH3)CH3), N,N-diglycidyl-4- glycidyloxyaniline (R4=OCH2CHOCH2, R5 and R6= OCH2CHOCH2 and N,N- diglycidylaniline (R4=H, R5 and R6= OCH2CHOCH2),. Also Ν,Ν-ethoxylated or N,N- propoxylated anilines, respectively ethoxylated or propoxylated toluidines may suitably be used and are considered to be encompassed in the group of suitable tertiary aromatic amines. It is obvious that especially the hydroxyl functional tertiary aromatic amines may be incorporated in a polymer. Preferred aromatic amines are the anilines and the toluidines.

The amount of tertiary aromatic amine (compound (c)) relative to the total amount of compound (a) and compound (b) is preferably from 0.01 to 10 wt.%, more preferably from 0.1 to 5 wt.%.

The unsaturated polyester resin composition according to the invention may further comprise (in)organic filler. The amount of inorganic and organic filler relative to the total amount of compounds (a) and (b) is preferably from 10 to 90 wt.%. Preferably, the composition comprises fibre as inorganic filler.

The unsaturated polyester resin composition according to the invention may further comprise a low profile additive. The amount of low profile additive relative to the total amount of compounds (a) and (b) is preferably from 20 to 70 wt.%.

The composition preferably further comprises a radical inhibitor. These radical inhibitors are preferably chosen from the group of phenolic compounds, benzoquinones, hydroquinones, catechols, stable radicals and/or phenothiazines. The amount of radical inhibitor that can be added may vary within rather wide ranges, and may be chosen as a first indication of the gel time as is desired to be achieved.

Suitable examples of radical inhibitors that can be used in the 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-butylcatechol, 4,6-di-t-butylcatechol, benzoquinone,

2,3,5,6-tetrachloro-1 ,4-benzoquinone, methylbenzoquinone,

2,6-dimethylbenzoquinone, napthoquinone, 1 -oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol (a compound also referred to as TEMPOL), 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one (a compound also referred to as TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine (a compound also referred to as 4-carboxy-TEMPO), 1-oxyl-2,2,5,5-tetramethylpyrrolidine,

1-oxyl-2,2,5,5-tetramethyl-3-carboxylpyrrolidine (also called 3-carboxy-PROXYL), galvinoxyl, aluminium-N-nitrosophenyl hydroxylamine, diethylhydroxylamine, phenothiazine and/or derivatives or combinations of any of these compounds.

Advantageously, the amount of radical inhibitor in the resin composition according to the invention (relative to the total amount of the composition) is in the range of from 0.0001 to 10 % by weight. More preferably, the amount of inhibitor in the 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 present invention further relates to a process for radically curing a resin composition according to the invention whereby the curing is effected in the presence of a peranhydride. The molar amount of peranhydride (compound (d)) relative to the molar amount of tertiary aromatic amine (compound (c)) is preferably from 0.05 to 10, more preferably from 0.1-5. The amount of peranhydride (compound (d)) relative to the total amount of compounds (a) and (b) is preferably from 0.01 to 30 wt.% and more preferably from 0.1 to 10 wt.%. A very suitable example of an aromatic peranhydride is dibenzoyl peroxide. A very suitable example of an aliphatic peranhydride is dilauroyl peroxide.

In a preferred embodiment, the process comprises adding the peranhydride to a composition comprising compounds (a), (b) and (c). Said adding is preferably done by mixing the peranhydride into the composition comprising compounds (a), (b) and (c).

The process according to the invention is preferably effected at a temperature in the range of from -20 to +150 °C, more preferably in the range of from -20 to +100 °C and even more preferably in the range of from -20 to + 40 °C.

The present invention further relates to a multicomponent system comprising an unsaturated polyester (a1) comprising building blocks according to formula (1) (ΛΛΛΛΛΛ/V

and, as monomer copolymerizable with said unsaturated polyester (a1), a monomer (b1) according to formula (2)

whereby n= 0-3; and R 2 each individually represent H, C C 2 o alkyl, C 3 -C 20 cycloalkyl, C 6 -C 2 o aryl, C 7 -C 20 alkylaryl or C 7 -C 20 arylalkyl; X = O, S or NR 3 whereby R 3 = H, Ci-C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, part of a polymer chain or attached to a polymer chain;

a tertiary aromatic amine (c),

and a peranhydride (d).

Preferred compounds (a), (b), (c) and (d) as well as the amounts are as described above. The system may further comprise additional compounds in amounts as described above.

The use of the multicomponent system according to the invention requires mixing of at least the compounds (a), (b) and (c) together with the

peranhydride (d) to obtain a cured network. As used herein, multicomponent systems means a system with at least two spatially separated components whereby the peranhydride is present in one component that does not comprise radical

copolymerizable compounds including compounds (a) and (b) in order to prevent premature radical copolymerization of the compounds (a) and (b) prior to the use of the multicomponent system to obtain the cured network. At the moment that the radically copolymerization of the compounds (a) and (b) is desired, at least a peranhydride (d) is added to this composition. Preferably, said adding is done by mixing the peranhydride into the composition comprising compounds (a), (b) and (c). The multicomponent system according to the invention comprises at least two components. ln one embodiment, the multicomponent system comprises at least three components I, II and III, whereby component I consists of a composition comprising compounds (a) and (b), component II consists of a composition comprising compound (c) and component III comprises the peranhydride (d).

In another embodiment, the system comprises at least two components I and II, whereby component I consists of a composition comprising compounds (a), (b) and (c) and component II comprises the peranhydride (d).

The present invention further relates to cured objects obtained by curing the resin composition according to the invention with a peranhydride or obtained by the process according to the invention or obtained by mixing the compounds of the multicomponent system as described above.

The present invention further relates to the use of such a cured structural part in automotive, boats, chemical anchoring, roofing, construction, containers, relining, pipes, tanks, flooring or windmill blades.

The invention is now demonstrated by means of a series of examples and comparative examples. All examples are supportive of the scope of claims. The invention, however, is not restricted to the specific embodiments as shown in the examples. Gel timer experiments

In some of the Examples and Comparative Experiments presented hereinafter, it is mentioned that curing was monitored by means of standard gel time equipment. This is intended to mean that both the gel time (T ge i or T25->35°c) and peak time (Tpea k or T 2 5-> P ea k ) and peak temperature were determined by exotherm

measurements according to the method of DIN 16945 when curing the resin with the peroxides as indicated in the Examples and Comparative Examples. The equipment used therefore was a Soform gel timer, with a Peakpro software package and National Instruments hardware; the waterbath and thermostat used were respectively Haake W26, and Haake DL30.

Preparation of unsaturated polyester resin (1) with itaconate building blocks

An unsaturated polyester was prepared by polycondensation of 198.5 parts of itaconic acid, 450.1 parts of phthalic anhydride, 351.4 parts of 1 ,3-propanediol. The starting compounds were charged into a reactor equipped with condenser, stirrer, a temperature control system and an inlet for nitrogen. Under a gentle flow of nitrogen, the reaction mixture was heated up and maintained at a temperature of 170-200°C. The acid value dropped slowly and at the end of the process vacuum was applied to help stripping the water from the reaction mixture to reach the targeted acid value. An acid value of 45.5 was reached. At the end of the polycondensation, 26 ppm hydroquinone and 84 ppm methyl hydroquinone were added. Gel permeation chromatography showed that the resin had a number-average molecular weight M n of 1055 g/mol and a polydispersity of 1.9 (column calibrated relative to polystyrene standards). Preparation of unsaturated polyester resin (2) with fumarate building blocks

An unsaturated polyester was prepared by polycondensation of 105 parts of maleic anhydride, 314 parts of phthalic anhydride, 244 parts of 1 ,2- propanediol. The starting compounds were charged into a reactor equipped with condenser, stirrer, a temperature control system and an inlet for nitrogen. Under a gentle flow of nitrogen, the reaction mixture was heated up and maintained at a temperature of 170-200°C. The acid value dropped slowly and at the end of the process vacuum was applied to help stripping the water from the reaction mixture to reach the targeted acid value. An acid value of 52 was reached. At the end of the polycondensation, 26 ppm hydroquinone and 84 ppm methyl hydroquinone were added. Gel permeation chromatography showed that the resin had a number-average molecular weight M n of 1214 g/mol and a polydispersity of 2.02 (column calibrated relative to polystyrene standards).

Example 1 and comparative example A

To 24 g of each of the unsaturated polyester (1) and (2) as described above, 16 g of a-methylene butyrolactone MBL was added and mixed. Next, 800 mg of accelerator NL-64-10P (a 10% Ν,Ν-diethyl aniline solution, Akzo Nobel) and 800 mg of Perkadox CH-50 L (50% dibenzoyl peroxide in phthalates, Akzo Nobel) were added and the curing was monitored in a standard gel timer equipment. Furthermore, 12 g of the mixture were poured into an aluminum dish for the determination of Barcol hardness of a 4 mm casting before and after postcure over night at 80°C. Table 1

Although in both Example 1 and Comparative Experiment A, an exotherm and a curing process was observed, only the small casting of Example 1 achieved a good hardness of the surface (Barcol). The casting of Comparative

Experiment A gave a very brittle material of which no hardness could be determined. The cured resin composition of both Example 1 and Comparative Experiment A were analyzed by IR. In Comp A, no crosslinking, i.e. copolymerization of fumarate unsaturations and MBL could be found, but the analysis indicated the

homopolymerization of MBL. In Example 1 , a copolymerization of itaconate

unsaturations and MBL leading to formation of a crosslinked network was observed. As a result, a non-brittle casting with good surface hardness was formed exclusively with the unsaturated polyester composition according to the invention. Example 2 and comparative experiments B1-B5

36 g of the itaconate unsaturated polyester resin (1) was diluted into 24 g of various reactive diluent mixtures (see Table 1). The viscosity of the resulting resin formulations was measured with a Brookfield viscosimeter CAP1000 at 25°C and 750 RPM with the appropriate cones. Next, 1.2 g NL-64-10P and 1.2 g Perkadox CH- 50 L were added. The curing was monitored using standard gel timer equipment. Small 4 mm castings were prepared by pouring 12 g of such a mixture in aluminum dishes in order to determine the hardness values and enable the curing in thinner layers. These castings were postcured at 80°C over night, then Barcol hardness on top and bottom of the castings was measured according to ASTM D2583. Table 2

MBL = a-methylene butyrolactone

BMA = n-butyl methacrylate

HPMA = 2-hydroxy propyl methacrylate

LMA = lauryl methacrylate

MMA= methyl methacrylate

This example and the comparative experiments clearly show that the reactive diluents according to formula (2) are well suited to be used in itaconate polyesters. From Table 2 it is clear that the reactive diluent MBL is a good alternative for styrene for unsaturated polyesters comprising itaconate building blocks since MBL (a) MBL is able to dilute the unsaturated polyester to a viscosity comparable to styrene and much better than the tested methacrylates (as indicated by the viscosity of the resin composition), (b) MBL has a good reacitivity with the unsaturated polyester (as indicated by the gel time) (c) curing the resin composition in the presence of a tertiary aromatic amine and a peranhydride can be effected efficiently (as indicated by the gel time, peak time and peak temperature). In addition, MBL has a lower volatily than styrene (as indicated by the higher boiling point). Furthermore, as clear from the results in the table, when using MBL as reactive diluent for an unsaturated polyester comprising itaconate building blocks, a good through curing (as indicated by both the peak temperature as well as the Barcol hardness at the bottom of the cup) and a good curing in air, as indicated by the Barcol of the air exposed surface (top), can be obtained. Examples 3-5 and comparative experiments C1-C12

To a mixture of 36 g itaconate unsaturated polyester resin (1) and 24 g MBL in a plastic beaker was added 800 mg of various amines and 800 mg of Perkadox CH-50 L in order to cure the mixtures in the beaker. The cure results are depicted in table 3.

Table 3

These examples and the comparative experiments clearly show that for a good and efficient curing of a formulation according to the invention a tertiary aromatic amine has to be used.

Examples 5, 6-7 and comparative experiments D1-D6

To a mixture of 36 g itaconate unsaturated polyester resin (1) and 24 g MBL in a plastic beaker was added 800 mg of Ν,Ν-dimethyl aniline and 800 mg of various peroxides in order to cure the mixtures in the beaker. The cure results are depicted in table 4.

Table 4

These examples and the comparative experiments clearly show that for a good and efficient curing of a formulation according to the invention a peranhydride has to be used.