(19)
(11)EP 2 742 055 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
16.10.2019 Bulletin 2019/42

(21)Application number: 12845143.2

(22)Date of filing:  10.08.2012
(51)International Patent Classification (IPC): 
C07D 493/04(2006.01)
C08F 224/00(2006.01)
C08F 220/32(2006.01)
C08F 236/14(2006.01)
C08F 124/00(2006.01)
C08F 122/20(2006.01)
C08F 222/20(2006.01)
(86)International application number:
PCT/US2012/050235
(87)International publication number:
WO 2013/066461 (10.05.2013 Gazette  2013/19)

(54)

PROCESS FOR PREPARING POLYMERS HAVING ENHANCED GLASS TRANSITION TEMPERATURES FROM RENEWABLE BIO-BASED (METH)ACRYLATED MONOMERS IN THE PRESENCE OF A VINYL ESTER RESIN MONOMER OR UNSATURATED POLYESTER MONOMER

VERFAHREN ZUR HERSTELLUNG VON POLYMEREN MIT ERHÖHTER GLASÜBERGANGSTEMPERATUR AUS BIOBASIERTEN ERNEUERBAREN (METH)ACRYLIERTEN MONOMEREN IN ANWESENHEIT VON VINYLESTERMONOMEREN ODER UNGESÄTTIGTEN POLYESTERMONOMEREN

PROCÉDÉ DE PRÉPARATION DE POLYMÈRES AYANT DES TEMPÉRATURES DE TRANSITION VITREUSE AUGMENTÉES À PARTIR DE MONOMÈRES (MÉTH)ACRYLÉS DE SOURCE BIO RENOUVELABLES ET DE MONOMÈRES D'ESTERS DE VINYLE OU DE POLYESTER INSATURÉ


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME

(30)Priority: 10.08.2011 US 201161521981 P

(43)Date of publication of application:
18.06.2014 Bulletin 2014/25

(73)Proprietors:
  • Drexel University
    Philadelphia, Pennsylvania 19104 (US)
  • THE UNITED STATES GOVERNMENT as represented by THE SECRETARY OF THE ARMY
    Washington, DC 20310 (US)

(72)Inventors:
  • PALMESE, Giuseppe R.
    Hainesport New Jersey 08036 (US)
  • LA SCALA, John Joseph
    Wilmington Delaware 19803 (US)
  • SADLER, Joshua Matthew
    Middle River Maryland 2122 (US)
  • LAM, Anh-Phuong Thy
    Newark Delaware 19713 (US)

(74)Representative: De Vries & Metman 
Overschiestraat 180
1062 XK Amsterdam
1062 XK Amsterdam (NL)


(56)References cited: : 
WO-A1-2011/048739
DE-C- 952 092
JP-A- 2003 306 490
US-A- 3 041 300
US-A1- 2009 018 300
WO-A2-2009/155020
GB-A- 586 141
JP-A- 2003 313 188
US-A- 3 272 845
US-B1- 7 723 461
  
  • JAN LUKASZCZYK ET AL: "Investigation on synthesis and properties of isosorbide based bis-GMA analogue", JOURNAL OF MATERIALS SCIENCE: MATERIALS IN MEDICINE, vol. 23, no. 5, 10 March 2012 (2012-03-10) , pages 1149-1155, XP055121115, ISSN: 0957-4530, DOI: 10.1007/s10856-012-4594-6
  • XU, MING-HUA ET AL.: 'Samarium diiodide induced asymmetric synthesis of ?- butyrolactone using chiral auxiliaries derived from isosorbide and isomannide.' CHINESE JOURNAL OF CHEMISTRY vol. 16, no. 6, 1998, pages 561 - 564, XP055143889
  • TAO XUCHEN ET AL.: 'Synthesis and characterization of a new liquid crystal polymer.' JOURNAL OF TEXTILE RESEARCH vol. 32, no. 1, 2011, pages 20 - 24, XP008173121
 
Remarks:
The file contains technical information submitted after the application was filed and not included in this specification
 
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description


[0001] The invention was reduced to practice with United States Government support under Cooperative Agreement no. W911NF-0-06-2-0013 with the U.S. Army Research Laboratory, the United States Government is therefore entitled to certain rights in this invention.

BACKGROUND OF THE INVENTION


1. Field of the Invention



[0002] The present invention relates to renewable vinyl ester resin systems made from bio-based monomers derived from non-petroleum celluloses or carbohydrates with a core scaffold of isosorbide, isomannide or isoidide.

2. Description of the Related Technology



[0003] Vinyl ester resins are thermosetting polymers that are commonly used in variety of applications ranging from adhesives to the resin matrices for fiber reinforced composites. There are many desirable features for vinyl ester resins, such as strength, toughness, low cost, low weight, and particular viscosities for processing, which are the reasons that vinyl ester resins have such wide acceptance in military and commercial uses.

[0004] Viscosity is a key factor for determining the utility of vinyl ester resins because lower viscosity resins are easier to work with and may be prepared using a larger range of methods. Petroleum-based vinyl ester resins are typically high molecular weight species that are often an extremely viscous fluids or solids. They require reactive diluents in order to reduce the resin viscosity so that the resins can be processed. Typical reactive diluents, such as styrene, are generally regarded as Hazardous Air Pollutants (HAPs) and/or Volatile Organic Compounds (VOCs) whose use is controlled by the Environmental Protection Agency (EPA). Large research efforts have been devoted to finding ways to eliminate or reduce the use of these highly hazardous reactive diluents.

[0005] Another factor that prevents vinyl ester resins' wider commercial use is that they are frequently derived from petroleum products. Petroleum is a commodity with well-known price volatility. The environmental costs of using petroleum are also very high.

[0006] Vinyl ester resins derived from renewable sources can reduce dependency on petroleum and have quickly become an imperative for continued use and development of thermosetting polymers and composites. Bio-refining of material based on converting biomass into vinyl ester products has been successfully developed. For example, bio-refining of triglycerides and carbohydrates have produced a wealth of new fine chemicals that are useful for the development of bio-based polymers. Fatty acids and triglycerides have also been successfully developed into materials ranging from toughening agents and plasticizers to reactive diluent replacements.

[0007] U.S. Patent no. 6,121,398 (Wool et al.) discloses functionalized triglycerides derived from plant oil that are polymerizable and their use to produce high modulus polymers. The functionalized triglycerides may be produced via several different chemical synthesis routes. For example, epoxidized triglyerides may be produced and converted to resilient rubbers by control of the molecular weight and cross-link density. The resultant rubbers can be used as rubber toughening agents in rigid composites. In the examples of this patent, acrylated base resins are prepared by reacting the epoxidized triglycerides with acrylic materials such as acrylic acid. The thermosetting resins prepared by this method are said to have properties similar to commercially available bisphenol-A vinyl ester resins. Other functionalized triglycerides are described in U.S. Patent 6,825,242 and U.S. patent application publication nos. US 2003/0139489 and US 2009/0275715.

[0008] Besides triglycerides, anhydrosugars derived from cellulose or carbohydrates, such as isosorbide, isomannide and isoidide, have also been explored for use as reactive monomers. These anhydrosugars are useful building blocks because they provide a rigid bicyclic core structure that can be developed into resins. For example, anhydrosugar, or bis-anhydrohexitols, have been fashioned into epoxy resins by forming the corresponding glycidyl ethers, as described in U.S. Patent no. 3,041,300 (Zech, et al.) and U.S. Patent no. 3,272,845 (Morrison, et al.). U.S. Patent no. 7,619,056 (Jaffe, et al.) describes a different synthesis process whereby the glycidyl ethers of these anhydrosugars can be obtained, and subsequently cured with polyamines to form thermosets. WO 2011/048739 A1 discloses (meth)acrylate monomers which have cyclic structures of the formula:

wherein each R1 is a hydrogen atom or (meth)acryloyl, with at least one R1 being (meth)acryloyl, A is a Cz_4 alkylene and n is a number from 0 to 30.

[0009] GB 586 141 A discloses a method wherein polyhydric alcohols or their anhydrides or hexose derivatives are treated in caustic soda solution with the acid chlorides of unsaturated acids or in pyridine solution with the anhydrides of the unsaturated acids to provide esters. The esters are then polymerized by heating for a few minutes to the melting point or any other suitable temperatures.

[0010] U.S. Patent no. 7,723,461 B1 discloses polymers including components produced from renewable resources and methods for making them. The polymers are made by polymerizing reactive intermediates derived from lactide or sorbitol with each other or with other resins. The intermediates can be used to prepare vinyl ester-styrene resins and thermoset networks formed therefrom.

[0011] However, anhydrosugars have not been successfully used to produce low viscosity thermosetting vinyl ester resins. Reactive diluents such as styrene are still commonly used for reducing viscosity of these bio-based resins. Commercial practice involves reducing the styrene content in the resin to about 33 wt% styrene, which makes the resin barely acceptable for composite manufacturing applications. In addition, reducing the styrene content significantly reduces the toughness of these resins.

[0012] Therefore, there is a need in the field to provide bio-based vinyl ester resins with excellent processability, acceptable toughness and a reduced dependency on reactive diluents.

SUMMARY OF THE INVENTION



[0013] In an aspect, the invention is directed to a copolymer as claimed in claim 13. In another aspect, the invention is directed to a method for making a polymer as claimed in claim 1 as well as to use of certain anhydrosugar based monomers to enhance the Tg of a polymer as claimed in claim 14.

[0014] The anhydrosugar-based monomers can be used as viscosity modulators and Tg enhancers in vinyl ester resins, thereby allowing a reduction in the reactive diluent concentration while maintaining suitable polymer toughness.

BRIEF DESCRIPTION OF THE DRAWING



[0015] FIG. 1 shows the synthetic routes for anhydrosugar-based monomers, using isosorbide as illustrative examples. Either isomannide or isoidide may be used in place of isosorbide in these synthetic routes.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)



[0016] For illustrative purposes, the principles of the present invention are described by referencing various exemplary embodiments. Although certain embodiments of the invention are specifically described herein, one of ordinary skill in the art will readily recognize that the same principles are equally applicable to, and can be employed in other systems and methods. Before explaining the disclosed embodiments of the present invention in detail, it is to be understood that the invention is not limited in its application to the details of any particular embodiment shown. Additionally, the terminology used herein is for the purpose of description and not of limitation. Furthermore, although certain methods are described with reference to steps that are presented herein in a certain order, in many instances, these steps may be performed in any order as may be appreciated by one skilled in the art; the novel method is therefore not limited to the particular arrangement of steps disclosed herein.

[0017] It must be noted that as used herein and in the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. Furthermore, the terms "a" (or "an"), "one or more" and "at least one" can be used interchangeably herein. The terms "comprising", "including", "having" and "constructed from" can also be used interchangeably.

[0018] In one aspect, anhydrosugar-based monomers for vinyl ester resin systems are disclosed. The monomers are derived from plant cellulose or carbohydrates, which are completely renewable sources. Eight of these monomers derived from isosorbide are shown in Figure 1 as Products 1-2 and Products 4-9. Other monomers are derived from isomannide or isoidide using the same synthetic routes. These monomers may be used as low viscosity cross-linkers for thermosetting vinyl ester resins, which can replace petroleum-based vinyl ester thermosetting resins for nearly all of their applications.

[0019] One important feature of these anhydrosugar-based monomers is their relatively low molecular weight due to their confined core structure resulting from the limited carbon chain length of these naturally occurring sugars. The low molecular weights of these anhydrosugar-based monomers can be used to reduce the overall viscosity of vinyl ester resins containing them, which, in turn, can reduce the dependency on reactive diluents. This has the advantage of reducing the use of reactive diluents, yet still producing vinyl ester resins with acceptable toughness and processability.

[0020] A number of different synthetic routes may be employed to produce these anhydrosugar-based monomers. Figure 1 shows some of the applicable synthetic routes, using isosorbide as illustrative example. Similar synthetic routes are available for the other two anhydrosugars: isomannide and isoidide. The starting materials, isosorbide, isomannide, or isoidide (Known 0 in Figure 1), are industrially refined from naturally occurring sugars by a two-step process: 1) reducing glucose, mannitose, or idose, respectively; and 2) subjecting the reduced glucose, mannitose or idose to an acid catalyzed dehydration to produce a fused bicyclic ring system. The anhydrosugars have formulae:



[0021] In synthetic route 1 of Figure 1, the anhydrosugars are acrylated to produce an acrylated monomer, Products 1 and 1a, which are capable of free radical polymerization. Products 1 and 1a have the formulae:

and



[0022] Several exemplary methods may be used to produce Product 1 from anhydrosugars. One method involves acylation of the hydroxyl groups of anhydrosugars using either acryloyl chloride or acryl anhydride and a base catalyst in an aprotic solvent. A second method involves esterification of anhydrosugars using acrylic acid, catalyzed using either acidic or basic conditions. A third method involves transesterification of anhydrosugars using methyl acrylate, catalyzed by either an acid or base catalyst. The reacting ester can be any combination of a parent acid that is an acrylate and a matching alcohol used to form the ester which is 1-8 carbon atoms in length. The small molecule alcohol of 1-8 carbon atoms is selected since it has a relatively low boiling point and can easily evaporate as the reaction progresses.

[0023] Synthetic route 2 of Figure 1 is similar to synthetic route 1 in that the anhydrosugars are functionalized using a variety of different methods to produce a methacrylated derivative, Products 2 and 2a, which are capable of free radical polymerization. Products 2 and 2a have the formulae:

and



[0024] Several exemplary methods may be used to produce Product 2 from anhydrosugars. One method involves acylation of the hydroxyl groups of anhydrosugars using either methacryloyl chloride or methacryl anhydride, catalyzed by a base catalyst in an aprotic solvent. A second method involves esterification of anhydrosugars using methacrylic acid, catalyzed by either acidic or basic conditions. A third method involves transesterification of anhydrosugars using methyl methacrylate, catalyzed by either an acid or base catalyst. The reacting ester can be any combination of a parent acid that is a methacrylate and a matching alcohol used to form the ester which is 1-8 carbon atoms in length. The small molecule alcohol of 1-8 carbon atoms is selected since it has a relatively low boiling point and can easily evaporate as the reaction progresses.

[0025] Synthetic route 3 of Figure 1 produces an intermediate referred to as Product 3 or Known 1. The formula of Product 3 is:



[0026] This process is well known in the art, as described in, for example, U.S. Patent no. 3,041,300 (Zech, et al.), U.S. Patent no. 3,272,845 (Morrison, et al.), and U.S. Patent no. 7,619,056 (Jaffe, et al.). Both of Products 4 and 5 are derived from this intermediate Known 1.

[0027] In synthetic route 4 of Figure 1, Known 1 is treated with acrylic acid in the presence of a chromium based catalyst, such as AMC-2™ (Aerojet chemicals, Rancho Cordova, CA). The reaction is carried out at 90-105 °C, with 2.0-5.0 wt % catalyst based on the total weight of the reaction mixture. Alternatively, the synthetic route 4 can be carried out using another suitable method. For example, reaction of Known 1 with acrylic acid in refluxing acetonitrile catalyzed with 12-25 mol % tetrabutylammonium bromide (TBAB), based on the number of moles of Known 1, will also result in Products 4 and 4a. This reaction can be monitored using acid number titrations until the desired acid number (AN) is reached and the reaction is complete. Another synthetic route for Products 4 and 4a is by a reaction between Known 0 of Figure 1 and glycidyl acrylate. Products 4 and 4a have the formulae:

and



[0028] In synthetic route 5 of Figure 1, Known 1 is treated with methacrylic acid in the presence of a chromium based catalyst, such as AMC-2™ (Aerojet chemicals, Rancho Cordova, CA). The reaction is carried out at 90-105 °C, with 2.0-5.0 wt % catalyst based on the total weight of the reaction mixture. Alternatively, Known 1 may be reacted with methacrylic acid in refluxing acetonitrile catalyzed with 12-25 mol % TBAB, based on the number of moles of Known 1. The resultant product is also Products 5 and 5a. This reaction can be monitored for completion using acid number titrations. Products 5 and 5a have the formulae:

and



[0029] Both of synthetic routes 4 and 5 open the epoxide rings on Known 1 to produce two free hydroxyl groups. These hydroxyl groups can be further functionalized with a number of different R groups. Examples of such R groups include acrylates, methacrylates, maleates, glycidyl ethers, or an alkyl, alkenyl or aryl substituent.

[0030] Synthetic route 6 of Figure 1 is maleination of Known 0, which results in Product 6. In an exemplary reaction, Known 0 and maleic anhydride are melted together to form a homogeneous solution before adding a base catalyst and stirring at 75-95 °C for 2-5 hours. Product 6 can be used as a cross-linking agent, or it can be used as an intermediate for synthetic routes 7 and 8. Product 6 has the formula:



[0031] Synthetic routes 7 and 8 in Figure 1 are analogous reactions wherein the treatment of Product 6 with a glycidyl vinyl ester, such as glycidyl acrylate or glycidyl methacrylate, produces Products 7 and 8, respectively. Use of the AMC-2™ catalyst in 0.5-3.0 wt% based on the total reaction mixture at low temperatures results in the formation of the desired product in excellent yields.

[0032] Alternatively, synthetic routes 7 and 8 can be carried out by TBAB catalyzed refluxing in acetonitrile. Reaction of Product 6 with a glycidyl vinyl ester, such as glycidyl acrylate or glycidyl methacrylate, in refluxing acetonitrile catalyzed with 2.5-20 mol % TBAB, based on the number of moles of Product 6, results in Products 7 and 8, respectively. This reaction can be monitored using acid number titrations until the desired acid number is reached and the reaction is complete. Product 7 has the formula:

Product 8 has the formula:



[0033] The reaction of Product 6 with glycidyl vinyl esters results in the opening of an epoxide ring and the formation of two free hydroxyl groups in Products 7 and 8. These hydroxyl groups can be further functionalized with a number of different R groups. Examples of such R groups include acrylates, methacrylates, maleates, glycidyl ethers, or an alkyl, alkenyl or aryl substituent.

[0034] Synthetic route 9 of Figure 1 is the dehydration of Known 0, where Known 0 is dissolved in solvent, preferably with a boiling point greater than 100 °C, with 5-35 mol %, based on the starting sugar, of acid catalyst and gently heated to between 50-80 °C to distill Product 9. Product 9 has the formula:



[0035] The anhydrosugar-based monomers have been characterized both chemically and physically. Infrared (IR) spectra for each individual monomer show absorbance peaks in the expected regions for key functional groups. Nuclear Magnetic Resonance (1H NMR) experiments have also been used for structure confirmation. Chemical shifts for 1H NMR peaks are in agreement for each monomer and appear as expected. Physical properties of these monomers have also been tested and found to have melting points ranging from and exhibited viscosities in the starting at 120 cP to being unmeasurable without the aid or reactive diluent. Overall, these anhydrosugar-based monomers are low-cost, have a low viscosity and low volatility and possess multiple polymerizable sites. These monomers are also reactive with other vinyl ester monomers.

[0036] The anhydrosugar-based monomers are ideally suited for use as vinyl ester cross-linkers. The anhydrosugar-based monomers exhibit suitable viscosities for producing new resins with low viscosity that require a minimal amount of reactive diluent. These anhydrosugar-based monomers can partially or completely replace petroleum-based cross-linkers used in the manufacture of vinyl ester resins. Preferably, the anhydrosugar-based monomeric cross-linkers are used as the only vinyl ester cross-linkers in the vinyl ester resin systems.

[0037] In another aspect of the present invention, the anhydrosugar-based monomers may be used as viscosity modulators. The anhydrosugar-based monomers have a confined core structure resulting from the limited carbon chain length of the naturally occurring sugars from which they are derived. The small core of these anhydrosugar monomers results in relatively low molecular weight anhydrosugar-based monomers that can be employed to reduce the overall viscosity of vinyl ester resins because of their low molecular weight in comparison with petroleum-based, relatively high molecule weight cross-linkers. Thus, the monomers are well-suited for modulating the viscosity of vinyl ester resins by varying the amount of anhydrosugar-based monomer used in blends with petroleum-based, high viscosity cross-linkers.

[0038] In yet another aspect of the present invention, the anhydrosugar-based monomers may be used as glass transition temperature (Tg) enhancers in vinyl ester resins to the desired level while also decreasing the viscosity. Because many of the bio-based reactive diluents have poor Tg's (homopolymers typically have Tg's below 0 °C), as compared to styrene, the anhydrosugar-based monomers of the present invention may be used to raise the Tg's of a resin system using bio-based reactive diluents without increasing the overall viscosity. On the other hand, the Tg of of vinyl ester resins increases as the anhydrosugar-based monomer concentration increases. Thus, the anhydrosugar-based monomers may be used as Tg enhancers for vinyl ester resin systems. The ideal Tg for vinyl ester resins can be varied over a wide range of, for example, 40 - 250 °C, depending on the intended end use and the temperatures at which the resins will be used. The amount of anhydrosugar-based monomer in a particular vinyl ester resin system may be varied in order to achieve the desired Tg for the vinyl ester resin.

[0039] Exemplary reactive diluents suitable for use in the present invention are petroleum-based and bio-based compounds with a single polymerizable site. Suitable petroleum-based reactive diluents include, but are not limited to, styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, aryl-methacrylates, aryl-acylates, aliphatic methacrylates, aliphatic acrylates. Suitable bio-based reactive diluents include, but are not limited to, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, furioc acid glycidyl methacrylate (FA-GM), furioc acid glycidyl acrylate and methacyrlated lauric acid, methacrylated octanoic acid, methacrylated fatty acids, and acrylated fatty acids.

[0040] A ternary resin system may also be formed by blending one or more anhydrosugar-based monomers with vinyl ester resins and reactive diluents. Ternary compositions will typically include up to 60%, more preferably, 5-15% by weight of reactive diluent(s) and 40-99%, more preferably, 85-95% by weight of vinyl ester cross-linker monomers, wherein the composition of the cross-linker monomers is 15-99% by weight anhydrosugar-based monomers and 1-70% by weight of vinyl ester resin and/or unsaturated polyester monomer, more preferably, 15-70% by weight anhydrosugar-based monomers and 30-70% by weight of vinyl ester resin and/or unsaturated polyester monomer, with the all weights being based on the weight of the product resin mixture. The unsaturated polyester monomer may be made from one or more of the following components: phthalic acid, terephthalic acid, m-phthalic acid, suberic acid, adipic acid, succinic acid, maleic acid, fumaric acid, butylene glycol, propylene glycol, and ethylene glycol, but is not limited to unsaturated polyesters made therefrom.

[0041] Other exemplary compositions comprise 5-95% by weight by weight of anhydrosugar-based monomers, 5-65% by weight of vinyl ester resin monomer and/or unsaturated polyester monomer and 0-50% by weight of at least one reactive diluent, or 15-90% by weight of anhydrosugar-based monomers, 10-55% by weight of vinyl ester resin monomer and/or unsaturated polyester monomer and 0-45% by weight of at least one reactive diluent. The vinyl ester resin is preferably a petroleum-based vinyl ester.

[0042] The vinyl ester resins of the present invention are used as monomers and include, but are not limited to, commercial vinyl esters, which are vinyl esters that are commercially available, and which may be derived from any source. A broad range of commercial vinyl esters are suitable for use in the ternary resin systems of the present invention. Some examples of suitable vinyl esters are methacrylated, acrylated glycidyl ethers of bisphenols and novolac vinyl esters. Suitable bisphenols include bisphenol A, hexafluorobisphenol A, bisphenol E, bisphenol F, tetramethyl bisphenol E, tetramethyl bisphenol F, bisphenol M, bisphenol C, bisphenol P and bisphenol Z. Methacrylates and acrylates of ethoxylated bisphenols may also be employed, as well as methacrylates of acrylates of epoxy products.

[0043] Vinyl esters with vinyl functionality greater than two may also be employed. Examples include acrylic and alkyl-acrylic vinyl esters of epoxy novolacs, and acrylates of tris-hydroxyphenylmethane glycidyl ether (THPM-GE), ethoxy phenol novolacs, and ethoxylated tris-hydroxyphenylmethane. In addition, brominated versions of the above systems, such as brominated bisphenol A based vinyl esters, may be employed. The preferred vinyl esters for use in the ternary systems of the present invention are the bisphenol vinyl esters due to the desirability of making structural composites from the resultant polymers.

[0044] In a ternary resin system, the anhydrosugar-based monomers of the present invention can be added to enhance the Tg of certain resins and/or to adjust the resin viscosity to improve the flow characteristics. The addition of the anhydrosugar-based monomers also increases the sustainability of the resins, and reduces the reliance on reactive diluents, such as styrene, while maintaining or improving on the properties of petroleum-based resins. Use of the anhydrosugar-based monomers in varying concentrations in relation to the petroleum-based vinyl ester and reactive diluents components can allow for the tailoring of the resin properties for specific applications and the tailoring of the properties of polymeric materials that result from these resins.

[0045] The resins containing the anhydrosugar-based monomers can be cured using any method that makes use of free-radically initiated reactive curing systems, including, but not limited to thermal cure, room temperature cure, electron beam cure, and ultraviolet cure.

[0046] The anhydrosugar-based monomers can be polymerized to form linear, branched, hyperbranched, and cross-linked polymers for a wide array of applications, including biosensors, rheology modifiers, biomaterials, and polymerizable surfactants for media encapsulation. The anhydrosugar-based monomers can also be used for the production of polymer matrix composites, which are used in military, automotive, recreational, and marine applications. Exemplary products that may be made from these polymer matrix composites include body panels and armor for vehicles, composite hoods, and boat hull structures. In addition, these polymer matrix composites can be used with traditional thermosetting vinyl and polyester resins as a gel coating material to provide a protective coating for composites and other surfaces.

[0047] The use of anhydrosugar-based monomers as vinyl ester cross-linkers, Tg enhancers and viscosity modulators has been tested experimentally and found to be successful. Thermosetting liquid molding resins using anhydrosugar-based monomers to replace some or all of the petroleum based vinyl ester, or unsaturated polyester resin cross-linkers, blended with common reactive diluents, have also been found to have acceptable resin viscosities and polymer mechanical properties similar to those of commercially available petroleum-based vinyl ester/styrene polymers.

EXAMPLES



[0048] The following examples are shown using isosorbide as the starting point of the synthesis of the anhydrosugar-based monomers. The isosorbide may be substituted with either isomannide or isoidide without any affect on the outcome of the reaction, yielding similar resin systems that result in comparable polymer systems.

Example 1



[0049] Stoichiometric amounts of isosorbide and triethyl amine were dissolved into dichloromethane and cooled to 0°C before slowly adding dropwise 2-2.5 molar equivalents of acryloyl chloride or methacryoyl chloride. The reaction mixture was slowly warmed to between 21-30°C and stirred for an additional 15-24 hours. This reaction was quenched with a saturated solution of sodium bicarbonate and then stirred vigorously for 20-45 minutes before partitioning the layers. The organic solution was sequentially washed with aqueous saturated sodium bicarbonate, water and aqueous saturated sodium chloride, dried over MgSO4 and the solvent was removed under reduced pressure. The product was a pale yellow to light brown oil. 1H NMR analysis showed that the degree of (meth)acrylation was 1.8-2.0 (meth)acrylate groups per molecule.

Example 2



[0050] Stoichiometric amounts of isosorbide and triethyl amine were dissolved into dichloromethane before adding a catalytic amount of dimethylaminopyridine (2.0-10.0 mol%) and cooling to 0°C. Once the reaction mixture reached the desired temperature, 2-2.5 molar equivalents of acrylic anhydride or methacrylic anhydride were slowly added dropwise. The reaction mixture was slowly warmed to between 21-30°C and stirred for an additional 15-24 hours. This reaction was quenched with a saturated solution of sodium bicarbonate and then stirred vigorously for 20-45 minutes before partitioning the layers. The organic solution was sequentially washed with aqueous saturated sodium bicarbonate, 1 M hydrochloric acid, water and aqueous saturated sodium chloride, dried over MgSO4 and the solvent was removed under reduced pressure. The product was a clear-colorless to pale yellow oil. 1H NMR analysis showed that the degree of (meth)acrylation was 1.8-2.0 (meth)acrylate groups per molecule.

Example 3



[0051] Isosorbide was melted at 68°C before adding hydroquinone (0.2 mol %) and 2.0-2.5 molar equivalents of acrylic acid or methacrylic acid. After the addition of a catalytic amount of acid, such as p-toluenesulfonic acid (0.5-2.5 wt %), the reaction temperature was raised to 130-145°C and the progress followed by acid number titrations. After 18-36 hours, the reaction mixture was cooled to room temperature and dissolved in ethyl acetate. The organic solution was washed sequentially with aqueous saturated sodium bicarbonate, water and aqueous sodium chloride and dried over MgSO4. The solvent was removed under reduced pressure and the product appeared as a pale yellow to light brown oil. 1H NMR analysis showed that the degree of (meth)acrylation was 1.7-2.0 (meth)acrylate groups per molecule.

Example 4



[0052] Isosorbide and 2-2.5 molar equivalents of either methyl acrylate or methyl methacrylate were melted together at 68°C before adding a free radical inhibitor (0.1 mol % of hydroquinone), and a catalytic amount of acid, such as p-toluenesulfonic acid (1.0-3.5 mol%). The temperature was raised to, and maintained at 85°C for 5-10 hours or until the reaction was complete. The product's appearance varied from a light to dark brown oil. 1H NMR analysis showed that the degree of (meth)acrylation was 1.5-1.8 (meth)acrylate groups per molecule.

Comparative Example 1



[0053] Neat monomer with a chemical structure similar to a vinyl ester, i.e. Product 2, was free-radically polymerized by the addition of 0.375 wt% Cobalt Naphthanate (CoNap) and 1.5 wt% Trigonox 239 A (Trigonox). The neat resin was purged with nitrogen prior to the addition of initiator and promoter for approximately 15 minutes to prevent oxygen inhibition during curing. The purged resin mixture with added initiator and promoter were poured into a silicone mold and allowed to cure at room temperature inside an oven with a constant low flow of nitrogen to avert oxygen inhibition.

Example 5



[0054] Neat monomer with chemical structure similar to polyester resin, i.e. Product 8, was free-radically polymerized with the addition of 0.375 wt% Cobalt Naphthanate (CoNap) and 1.5 wt% methyl ethyl ketone peroxide (MEKP). The neat resin was purged with nitrogen prior to the addition of initiator and promoter for approximately 15 minutes to prevent oxygen inhibition during curing. The purged resin mixture with added initiator and promoter were poured into a silicone mold and allowed to cure at room temperature inside an oven with a constant low flow of nitrogen to avert oxygen inhibition.

Comparative Example 2



[0055] The rheological and thermomechanical properties of Product 2 were tested as a neat monomer. Product 2 exhibited a Newtonian viscosity of approximately 120 cP at 25°C. Following curing by the procedure described in Example 5, the cured monomer was free-radically polymerized at room temperature and post cured at 180°C for 2 hours. Dynamic Mechanical Analysis (DMA) showed a Tg of approximately 250°C and a storage modulus of 2,900 MPa at 25°C.

Comparative Example 3



[0056] A partial bio-based monomer blend was formulated in a ratio of 35:65 wt% of styrene, as a reactive diluent, to Product 2, as a cross-linker, respectively. The formulated monomer blend had a Newtonian viscosity of 5 cP at 25°C. Following curing by the procedure described in Example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 190°C for 2 hours. DMA results showed a Tg of approximately 212°C and a storage modulus of 3,234 MPa at 25°C.

Example 6



[0057] A partial bio-based three-component monomer blend was formulated in a ratio of 10:80:10 wt% of Product 2, methacrylated epoxy RDX 26936 (RDX), as a vinyl ester resin mixture, and styrene, as a reactive diluent, respectively. The formulated monomer blend had a Newtonian viscosity of 8,981 cP at 25°C. Following curing by the procedure described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 190°C for 2 hours. DMA results showed a Tg of approximately 145°C and a storage modulus of 2,893 MPa at 25°C.

Example 7



[0058] A partial bio-based three-component monomer blend was formulated in a ratio of 50:40:10 wt% of Product 2, RDX, as a vinyl ester resin mixture, and styrene, as a reactive diluent, respectively. The formulated three-component monomer blend had a Newtonian viscosity of 480 cP at 25°C. Following curing by the method described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 200°C for 2 hours. DMA results showed a Tg of approximately 169°C and a storage modulus of 2,893 MPa at 25°C.

Example 8



[0059] A partial bio-based three-component monomer blend was formulated in a ratio of 80:10:10 wt% of Product 2, RDX, as a vinyl ester resin mixture, and styrene, as a reactive diluent, respectively. The formulated three-component monomer blend had a Newtonian viscosity of 68 cP at 25°C. Following curing by the method described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 190°C for 2 hours. DMA results showed a Tg of approximately 244°C and a storage modulus of 3,352 MPa at 25°C.

Comparative Example 4



[0060] A bio-based monomer blend was formulated in a ratio of 35:65 wt% of furfuryl methacrylate, as a reactive diluent, to Product 2, as a cross-linker, respectively. The formulated monomer blend had a Newtonian viscosity of 16 cP at 25°C. Following curing by the method described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 145°C for 2 hours. DMA results showed a Tg of approximately 122°C and a storage modulus of 3,421 MPa at 25°C.

Example 9



[0061] A bio-based three-component monomer blend was formulated in a ratio of 10:80:10 wt% of Product 2, RDX, as a vinyl ester resin mixture, and furfuryl methacrylate, as a reactive diluent, respectively. The formulated three-component monomer blend had a Newtonian viscosity of 22,830 cP at 25°C. Following curing by the procedure described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 170°C for 2 hours. DMA results showed a Tg of approximately 128°C and a storage modulus of 3,404 MPa at 25°C.

Example 10



[0062] A bio-based vinyl ester ternary monomer system was formulated in a ratio of 50:40:10 wt% of Product 2, RDX, as a vinyl ester resin mixture, and furfuryl methacrylate respectively. The formulated monomer blend had a Newtonian viscosity of 701 cP at 25°C. Following curing by the procedure described in example 5, the cured, bio-based three-component monomer blend was free-radically polymerized at room temperature and post cured at 195°C for 2 hours. DMA results showed a Tg of approximately 157°C and a storage modulus of 3,525 MPa at 25°C.

Example 11



[0063] A bio-based vinyl ester three-component monomer blend was formulated in a ratio of 80:10:10 wt% of Product 2, RDX, as a vinyl ester resin mixture, and furfuryl methacrylate respectively. The formulated three-component monomer blend had a Newtonian viscosity of 92 cP at 25°C. Following curing by the procedure described in example 5, the cured, bio-based three-component monomer blend was free-radically polymerized at room temperature and post cured at 190°C for 2 hours. DMA results showed a Tg of approximately 263°C and a storage modulus of 3,455 MPa at 25°C.

Comparative Example 5



[0064] A bio-based two-component monomer blend was formulated in a ratio of 35:65 wt% of methacrylated lauric acid (MLau) to Product 2 respectively. The formulated monomer blend had a Newtonian viscosity of 73 cP. Following curing by the method described in example 5, the cured, bio-based two-component monomer blend was free-radically polymerized at room temperature and post cured at 110°C for 2 hours. DMA results showed a Tg of approximately 107°C and a storage modulus of 2,220 MPa at 25°C.

Example 12



[0065] A bio-based vinyl ester three-component monomer blend was formulated in a ratio of 10:80:10 wt% of Product 2, RDX, as a vinyl ester resin mixture, and MLau respectively. The formulated three-component monomer blend had a Newtonian viscosity of 58,995 cP at 25°C. Following curing by the procedure described in example 5, the cured, bio-based three-component monomer blend was free-radically polymerized at room temperature and post cured at 160°C for 2 hours. DMA results showed a Tg of approximately 169°C and a storage modulus of 3,322 MPa at 25°C.

Example 13



[0066] A bio-based vinyl ester three-component monomer blend was formulated in a ratio of 50:40:10 wt% of Product 2, RDX, as a vinyl ester resin mixture, and MLau respectively. The formulated three-component monomer blend had a Newtonian viscosity of 1,445 cP at 25°C. Following curing by the procedure described in example 5, the cured, bio-based three-component monomer blend was free-radically polymerized at room temperature and post cured at 180°C for 2 hours. DMA results showed a Tg of approximately 165°C and a storage modulus of 3,206 MPa at 25°C.

Example 14



[0067] A bio-based vinyl ester three-component monomer blend was formulated in a ratio of 80:10:10 wt% of Product 2, RDX, as a vinyl ester resin mixture, and MLau respectively. The formulated three-component monomer blend had a Newtonian viscosity of 153 cP at 25°C. Following curing by the procedure described in example 5, the cured, bio-based three-component monomer blend was free-radically polymerized at room temperature and post cured at 125°C for 2 hours. DMA results showed a Tg of 193°C and a storage modulus of 2,927 MPa at 25°C.

Example 15



[0068] A partial bio-based monomer blend was formulated in a ratio of 80:20 wt% Product 2, as a viscosity modulator, to Viapal™ 450 Unsaturated Polyester Resin (UPE), as a cross-linker, respectively. The formulated monomer blend had a Newtonian viscosity of 1,098 cP at 25°C. Following curing by the procedure described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 110°C for 2 hours. DMA results showed a Tg of approximately 58°C and a storage modulus of 3,623 MPa at 25°C.

Example 16



[0069] A partial bio-based three-component monomer blend was formulated in a ratio of 50:40:10 wt% of Product 2, UPE, as a resin mixture, and furfuryl methacrylate (FM), as a reactive diluent, respectively. The formulated three-component monomer blend had a Newtonian viscosity of 700 cP at 25°C. Following curing by the method described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 110°C for 2 hours. DMA results showed a Tg of approximately140 °C and a storage modulus of 157 MPa at 25°C.

Example 17



[0070] A partial bio-based monomer blend was formulated in a ratio of 50:50 wt% of Product 2, as a viscosity modulator, to RDX, as a cross-linker, respectively. Following curing by the procedure described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 110 °C for 2 hours. DMA results showed a Tg of approximately 130 °C and a storage modulus of 3200 MPa at 25 °C.

Example 18



[0071] A partial bio-based monomer blend was formulated in a ratio of 80:20 wt% of Product 2, as a viscosity modulator, to RDX, as a cross-linker, respectively. Following curing by the procedure described in example 5, the cured monomer blend was free-radically polymerized at room temperature and post cured at 110 °C for 2 hours. DMA results showed a Tg of approximately 212 °C and a storage modulus of 3100 MPa at 25 °C.


Claims

1. A method of making a polymer comprising the step of curing a composition comprising at least one anhydrosugar-based monomer selected from monomers with structures of:





and

and at least one vinyl ester resin monomer or unsaturated polyester monomer, and optionally a reactive diluent,

wherein the composition includes 1-99% by weight of anhydrosugar-based monomers, 1-70% by weight of vinyl ester resin monomer or unsaturated polyester monomer, and 0-60% by weight of at least one reactive diluent, all weight percentages are based on the weight of the composition.


 
2. The method of claim 1, wherein the composition comprises 5-95% by weight of anhydrosugar-based monomers, 5-65% by weight of vinyl ester resin monomer or unsaturated polyester monomer and 0-50% by weight of at least one reactive diluent.
 
3. The method of claim 1, wherein the composition comprises 15-90% by weight of anhydrosugar-based monomers, 10-55% by weight of vinyl ester resin monomer or unsaturated polyester monomer and 0-45% by weight of at least one reactive diluent.
 
4. The method of claim 1, wherein the composition comprises 40-99% by weight of a cross-linker monomer composition, and 0-60% by weight of a reactive diluent, based on a total weight of the curable composition, wherein the cross-linker monomer composition is 15-99% by weight of the anhydrosugar-based monomer and 1-70% by weight of the vinyl ester resin or unsaturated polyester monomer.
 
5. The method of claim 1, wherein the composition comprises 40-99% by weight of a cross-linker monomer composition, and 0-60% by weight of a reactive diluent, based on a total weight of the curable composition, wherein the cross-linker monomer composition is 15-70% by weight of the anhydrosugar-based monomer and 30-70% by weight of the vinyl ester resin or unsaturated polyester monomer.
 
6. The method of any one of claims 1-5, wherein the reactive diluent is selected from the group consisting of: styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, furfuryl methacrylate, methacrylated lauric acid and methacrylated fatty acids.
 
7. The method of claim 6 comprising the vinyl ester monomer, wherein the vinyl ester monomer is selected from the group consisting of (meth)acrylated glycidyl ethers of bisphenols, (meth)acrylated ethoxylated bisphenols and novolac vinyl esters.
 
8. The method of claim 7, wherein the bisphenols are selected from the group consisting of: bisphenol A, hexafluorobisphenol A, bisphenol E, bisphenol F, tetramethyl bisphenol E, tetramethyl bisphenol F, bisphenol M, bisphenol C, bisphenol P and bisphenol Z.
 
9. The method of claim 6 comprising the unsaturated polyester monomer, wherein the unsaturated polyester monomer is made from one or more of the following components: phthalic acid, terephthalic acid, m-phthalic acid, suberic acid, adipic acid, succinic acid, maleic acid, fumaric acid, butylene glycol, propylene glycol, and ethylene glycol.
 
10. The method of any one of claims 1-9 wherein the curing employs a free-radical initiated reactive curing system, preferably a thermal cure, a room temperature cure, an electron beam cure or an ultraviolet cure.
 
11. The method of any one of claims 1-10, wherein the monomer is selected from a monomer of the formula 1 and a monomer of the formula 1a.
 
12. The method of any one of claims 1-10, wherein the monomer is selected from a monomer of the formula 2 and a monomer of the formula 2a.
 
13. A copolymer obtainable by the method of any one of claims 1-12.
 
14. Use of at least one anhydrosugar-based monomer selected from monomers with structures of:





and

to enhance the glass transition temperature of a vinyl ester resin polymer.
 


Ansprüche

1. Verfahren zum Herstellen eines Polymers, umfassend den Schritt des Härtens einer Zusammensetzung, umfassend
mindestens ein Monomer auf Zuckeranhydrid-Basis, ausgewählt aus Monomeren mit Strukturen von:





und



und mindestens ein Vinylesterharz-Monomer oder ungesättigtes Polyestermonomer und gegebenenfalls ein reaktives Verdünnungsmittel,

wobei die Zusammensetzung 1 bis 99 % Massenanteil Monomere auf Zuckeranhydrid-Basis, 1 bis 70 % Massenanteil Vinylesterharz-Monomer oder ungesättigtes Polyestermonomer und 0 bis 60 % Massenanteil mindestens eines reaktiven Verdünnungsmittels beinhaltet, wobei sich alle Massenanteilsprozente auf die Masse der Zusammensetzung beziehen.


 
2. Verfahren nach Anspruch 1, wobei die Zusammensetzung 5 bis 95 % Massenanteil Monomere auf Zuckeranhydrid-Basis, 5 bis 65 % Massenanteil Vinylesterharz-Monomer oder ungesättigtes Polyestermonomer und 0 bis 50 % Massenanteil mindestens eines reaktiven Verdünnungsmittels umfasst.
 
3. Verfahren nach Anspruch 1, wobei die Zusammensetzung 15 bis 90 % Massenanteil Monomere auf Zuckeranhydrid-Basis, 10 bis 55 % Massenanteil Vinylesterharz-Monomer oder ungesättigtes Polyestermonomer und 0 bis 45 % Massenanteil mindestens eines reaktiven Verdünnungsmittels umfasst.
 
4. Verfahren nach Anspruch 1, wobei die Zusammensetzung 40 bis 99 % Massenanteil einer Vernetzermonomer-Zusammensetzung und 0 bis 60 % Massenanteil eines reaktiven Verdünnungsmittels, bezogen auf eine Gesamtmasse der härtbaren Zusammensetzung, umfasst, wobei die Vernetzermonomer-Zusammensetzung 15 bis 99 % Massenanteil des Monomers auf Zuckeranhydrid-Basis und 1 bis 70 % Massenanteil des Vinylesterharzes oder des ungesättigten Polyestermonomers beträgt.
 
5. Verfahren nach Anspruch 1, wobei die Zusammensetzung 40 bis 99 % Massenanteil einer Vernetzermonomer-Zusammensetzung und 0 bis 60 % Massenanteil eines reaktiven Verdünnungsmittels, bezogen auf eine Gesamtmasse der härtbaren Zusammensetzung, umfasst, wobei die Vernetzermonomer-Zusammensetzung 15 bis 70 % Massenanteil des Monomers auf Zuckeranhydrid-Basis und 30 bis 70 % Massenanteil des Vinylesterharzes oder des ungesättigten Polyestermonomers beträgt.
 
6. Verfahren nach einem der Ansprüche 1 bis 5, wobei das reaktive Verdünnungsmittel ausgewählt ist aus der Gruppe bestehend aus Styrol, 2-Hydroxymethacrylat, Methylmethacrylat, Methylacrylat, Furfurylmethacrylat, methacrylierter Laurinsäure und methacrylierten Fettsäuren.
 
7. Verfahren nach Anspruch 6, umfassend das Vinylester-Monomer, wobei das Vinylester-Monomer ausgewählt ist aus der Gruppe bestehend aus (meth)acrylierten Glycidylethern von Bisphenolen, (meth)acrylierten ethoxylierten Bisphenolen und Novolak-Vinylestern.
 
8. Verfahren nach Anspruch 7, wobei die Bisphenole ausgewählt sind aus der Gruppe bestehend aus Bisphenol A, Hexafluorbisphenol A, Bisphenol E, Bisphenol F, Tetramethylbisphenol E, Tetramethylbisphenol F, Bisphenol M, Bisphenol C, Bisphenol P und Bisphenol Z.
 
9. Verfahren nach Anspruch 6, umfassend das ungesättigte Polyestermonomer, wobei das ungesättigte Polyestermonomer aus einer oder mehreren der folgenden Bestandteile hergestellt ist: Phthalsäure, Terephthalsäure, m-Phthalsäure, Octandisäure, Adipinsäure, Bernsteinsäure, Maleinsäure, Fumarsäure, Butylenglykol, Propylenglykol und Ethylenglykol.
 
10. Verfahren nach einem der Ansprüche 1 bis 9, wobei das Härten ein durch freie Radikale eingeleitetes reaktives Härtungssystem verwendet, vorzugsweise eine thermische Härtung, eine Raumtemperaturhärtung, eine Elektronenstrahlhärtung oder eine Ultravioletthärtung.
 
11. Verfahren nach einem der Ansprüche 1 bis 10, wobei das Monomer ausgewählt ist aus einem Monomer der Formel 1 und einem Monomer der Formel 1a.
 
12. Verfahren nach einem der Ansprüche 1 bis 10, wobei das Monomer ausgewählt ist aus einem Monomer der Formel 2 und einem Monomer der Formel 2a.
 
13. Ein Copolymer, erhältlich durch das Verfahren nach einem der Ansprüche 1 bis 12.
 
14. Verwendung von mindestens einem Monomer auf Zuckeranhydrid-Basis, ausgewählt aus Monomeren mit Strukturen von:





und

um die Glasübergangstemperatur eines Vinylesterharz-Polymers zu erhöhen.
 


Revendications

1. Procédé de fabrication d'un polymère comprenant l'étape consistant à durcir une composition comprenant au moins un monomère à base d'anhydro-sucre choisi parmi des monomères ayant des structures selon :





et

et au moins un monomère de résine d'ester de vinyle ou monomère polyester insaturé, et éventuellement un diluant réactif,

la composition incluant de 1 à 99 % en poids de monomères à base d'anhydro-sucre, de 1 à 70 % en poids de monomère de résine d'ester de vinyle ou de monomère polyester insaturé et de 0 à 60 % en poids d'au moins un diluant réactif, tous les pourcentages en poids étant basés sur le poids de la composition.


 
2. Procédé selon la revendication 1, dans lequel la composition comprend de 5 à 95 % en poids de monomères à base d'anhydro-sucre, de 5 à 65 % en poids de monomère de résine d'ester de vinyle ou de monomère polyester insaturé et de 0 à 50 % en poids d'au moins un diluant réactif.
 
3. Procédé selon la revendication 1, dans lequel la composition comprend de 15 à 90 % en poids de monomères à base d'anhydro-sucre, de 10 à 55 % en poids de monomère de résine d'ester de vinyle ou monomère polyester insaturé et de 0 à 45 % en poids d'au moins un diluant réactif.
 
4. Procédé selon la revendication 1, dans lequel la composition comprend de 40 à 99 % en poids d'une composition de monomères de réticulation et de 0 à 60 % en poids d'un diluant réactif, sur la base d'un poids total de la composition durcissable, la composition de monomères de réticulation étant de 15 à 99 % en poids du monomère à base d'anhydro-sucre et de 1 à 70 % en poids du monomère de résine d'ester de vinyle ou polyester insaturé.
 
5. Procédé selon la revendication 1, dans lequel la composition comprend de 40 à 99 % en poids d'une composition de monomères de réticulation et de 0 à 60 % en poids d'un diluant réactif, sur la base d'un poids total de la composition durcissable, la composition de monomères de réticulation étant de 15 à 70 % en poids du monomère à base d'anhydro-sucre et de 30 à 70 % en poids du monomère de résine d'ester de vinyle ou polyester insaturé.
 
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le diluant réactif est choisi dans le groupe constitué de : styrène, 2-hydroxyméthacrylate, méthacrylate de méthyle, méthacrylate de furfuryle, acide laurique méthacrylé et acides gras méthacrylés.
 
7. Procédé selon la revendication 6 comprenant le monomère ester de vinyle, le monomère ester de vinyle étant choisi dans le groupe constitué d'éthers de glycidyle (méth)acrylés de bisphénols, de bisphénols éthoxylés (méth)acrylés et d'esters de vinyle novolaques.
 
8. Procédé selon la revendication 7, dans lequel les bisphénols sont choisis dans le groupe constitué de : bisphénol A, hexafluorobisphénol A, bisphénol E, bisphénol F, bisphénol E tétraméthylique, bisphénol F tétraméthylique, bisphénol M, bisphénol C, bisphénol P et bisphénol Z.
 
9. Procédé selon la revendication 6 comprenant le monomère polyester insaturé, le monomère polyester insaturé étant constitué d'un ou plusieurs des constituants suivants : acide phtalique, acide téréphtalique, acide m-phtalique, acide subérique, acide adipique, acide succinique, acide maléique, acide fumarique, butylène glycol, propylène glycol et éthylène glycol.
 
10. Procédé selon l'une quelconque des revendications 1 à 9 dans lequel le durcissement emploie un système de durcissement réactif à initiation par les radicaux libres, de préférence un durcissement thermique, un durcissement à température ambiante, un durcissement par faisceau électronique ou un durcissement par les ultraviolets.
 
11. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le monomère est choisi parmi un monomère de formule 1 et un monomère de formule la.
 
12. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le monomère est choisi parmi un monomère de formule 2 et un monomère de formule 2a.
 
13. Copolymère pouvant être obtenu par le procédé selon l'une quelconque des revendications 1 à 12.
 
14. Utilisation d'au moins un monomère à base d'anhydro-sucre choisi parmi des monomères ayant des structures selon :





et

pour augmenter la température de transition vitreuse d'un polymère de résine d'ester de vinyle.
 




Drawing








Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description