(19)
(11)EP 3 351 572 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.07.2020 Bulletin 2020/31

(21)Application number: 18154334.9

(22)Date of filing:  24.02.2012
(51)International Patent Classification (IPC): 
C08G 18/28(2006.01)
C08G 18/67(2006.01)
C08G 18/81(2006.01)
C07D 263/02(2006.01)
C07D 263/18(2006.01)
C08G 18/32(2006.01)
C08G 18/80(2006.01)
C08G 73/06(2006.01)
C07D 413/06(2006.01)
C07D 263/24(2006.01)

(54)

PROCESS AND COMPOSITION OF MAKING POLYMERIZABLE RESINS CONTAINING OXAZOLIDONE

VERFAHREN UND ZUSAMMENSETZUNG ZUR HERSTELLUNG POLYMERISIERBARER HARZE MIT OXAZOLIDON

PROCÉDÉ ET COMPOSITION DE FABRICATION DE RÉSINES POLYMÉRISABLES CONTENANT UNE OXAZOLIDONE


(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

(30)Priority: 25.02.2011 US 201161446522 P
25.03.2011 US 201161467425 P

(43)Date of publication of application:
25.07.2018 Bulletin 2018/30

(62)Application number of the earlier application in accordance with Art. 76 EPC:
12709200.5 / 2678366

(73)Proprietor: Dentsply Sirona Inc.
York, PA 17401-2991 (US)

(72)Inventor:
  • JIN, Xiaoming
    Middletown, Delaware 19709 (US)

(74)Representative: Schiener, Jens 
Wächtershäuser & Hartz Patentanwaltspartnerschaft mbB Weinstraße 8
80333 München
80333 München (DE)


(56)References cited: : 
US-A- 4 022 721
US-A- 5 686 541
  
  • THOMAS FRANCIS ET AL: "carbamates and 2-oxazolidinones from tertiary alcohols and isocyanates", CANADIAN JOURNAL OF CHEMISTRY, NATIONAL RESEARCH COUNCIL. OTTAWA; CA, vol. 54, 1 January 1976 (1976-01-01), pages 24-30, XP009111686,
  
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

BACKGROUND



[0001] Isocyanate is a very versatile reactive group to yield a variety of linkages (see Scheme I), which have been widely utilized in organic preparations and polymer synthesis.

[0002] Linear polyurethane is readily prepared by reacting diisocyanate and diol and polyurea would be resulted if diisocyanate reacts with diamine instead. On the other hand, when isocyanate reacts with epoxide (Scheme II), it yields an oxazolidone derivative. Oxazolidone is a five-member heterocyclic urethane, which should impart chain rigidity and excellent thermal properties to the corresponding polymers. Polymers bearing oxazolidone in both main-chain and side-chain may be synthesized in different approaches; the most convenient method is the process from isocyanate and epoxide. This process of forming oxazolidone-containing polymers depends on several factors, such as catalysts, temperature, and the type and ratio of the reactants.

[0003] It is known to prepare poly-2-oxazolidones from diepoxides and diisocyanates by using different catalysts, which include halides of the alkali and alkaline earth metals and the metals of third group of the periodic system, such as LiCl, MgCl2, FeCl3, AlCl3, ZnCl2, quarternary ammonium salts, such as (CH3)4NI and (C2H5)4NBr, complexes of the Lewis acid-Lewis base type, such as LiCl-HMPA, MgCl-HMPA, AICI3-tris(2-ethylhexyl)phosphine oxide, alcoholates of the alkali metals, alkaline earth metals, such as LiOBu, NaOBu, Mg(OPh)2, Al(OPh)3, and metal-organic compounds of the type ZnR2, Zn(OCOR)2, AlR3 were also used in the past.
US 5,686,541 A and US 4,022,721 A disclose stress reduced resins on the basis of oxazolidones, which are obtained from polyisocyanates and epoxy resins.

Francis T. et al, Can. J. Chem. 54, pages 24-30 (1976) discloses carbamates and 2-oxazolidinones from tertiary alcohols and isocyanates.


BRIEF DESCRIPTION OF THE DRAWINGS



[0004] 

Figure 1 demonstrates that when a conventional stress reduced resin (SDR) was thermally aged at different temperatures, ranging from 3°C, 25°C, 37°C, to 45°C, for a variable of time (up to 500 days), respectively, that the increasing viscosity of such thermally aged SDR resin becomes evident.

Figure 2 demonstrates that when conventional stress reduced resin (SDR) was aged at room temperature (about 25°C) in the presence of an acidic monomer resin, such as PENTA, for a variable of time (up to 500 days), a viscosity increase similar to the viscosity increase to thermally aged stress reduced resin (SDR) occurred. In addition.

Figure 3a demonstrates FTIR spectra for thermally transformed urethane polymerizable resin.

Figure 3b demonstrates FTIR spectra of thermally transformed urethane model compound (HPN-HMDI-HPN).

Figure 4a demonstrates 13C NMR full spectra of thermally transformed urethane model compound (HPN-HMDI-HPN).

Figure 4b demonstrates 13C NMR partial spectra of thermally transformed urethane model compound (HPN-HMDI-HPN).


SUMMARY


The present invention relates to the subject matter of claims 1 to 5.



[0005] Disclosed herein are a process and composition to make polymerizable resins containing oxazolidone, in which organic acid-catalyzed and/or thermal annealing process got involved and consequently promoted a unique intramolecular transformation from a linear urethane linkage to a cyclic urethane linkage for those specifically constructed urethane resins containing α-substituted β-ketone moieties. Thus polymerizable resin bearing oxazolidone moiety is readily resulted under mild conditions. In addition, the increasing chain rigidity due to the oxazolidone moiety in the resulting resins offer improved thermal stability and mechanical strength. Furthermore, this disclosure also presents an effective approach to modifying the resin's viscosity without involving any forms of polymerization.

[0006] Urethane-based polymers and oligomeric resins have recently received considerable consideration, especially in biomedical and restorative dentistry. However, it remains highly desirable to further enhance the physical and mechanical performance of urethane-based materials. Obviously, oxazolidone-based urethane should be a reasonable solution to such a demand. Unfortunately, current processes of forming oxazolidone requires fairly harsh conditions such as high temperature, that is, temperatures above about 200°C, and catalysts, which also promote undesired side reactions.

[0007] In order to overcome these deficiencies of making oxazolidone derivatives, especially for those resins bearing additional polymerizable groups, such as vinyl and (meth) acrylate, the present disclosure provides mild processes for making polymerizable resins containing an oxazolidone moiety.

[0008] Specifically, disclosed herein is a polymerizable resin comprising structurally specific urethane linkages, which readily undergo intramolecular cyclization to yield oxazolidone moieties under mild processing conditions. Accordingly, the less stable groups are able to remain intact or polymerizable. Furthermore, another aspect of present disclosure is that viscosity of the disclosed polymerizable resin can be readily modified.








DETAILED DESCRIPTION



[0009] Disclosed herein are processes to prepare a polymerizable resin that contains cyclic urethane linkage or oxazolidone moiety. The disclosed processes include at least two steps: (1) reacting at least two isocyanates, such as 1, 6-hexane diisocyanate(HMDI) and a structurally specific α-disubstituted β-phenone hydroxyl compounds (as shown in Scheme IIIa and IIIb), to form a linear condensate, and (2) converting the linear urethane precursors into an oxazolidone-based resin or polymer. The conversion of the linear condensate is induced by thermally annealing the precursors at temperature of from 25°C to 150°C.

[0010] During the development of low stress resin, stress reduced resin (SDR), as described in co-owned U.S. Patent Application Publication No. 2008/0076853 and U.S. Patent Application Publication No. 2008/0076848, it was surprisingly noted that thermal aging, or annealing, at different temperatures could cause substantial viscosity increases (as shown in Fig. 1) in the SDR resin. However, the structural analysis indicated that there was no evidence related to the involvement of the methacrylate to the viscosity building up.

[0011] Recently, in the pursuit of the process disclosed herein, it was discovered that a unique linear urethane linkage in a resin could cause the substantial viscosity increases. Specifically, the linear urethane linkage composed of an adduct of diisocyanates, such as HMDI or TMDI, and a special diol that features α-substituted β-ketone moiety and hydroxylated methacrylate provided the viscosity change.

[0012] Further structural analysis confirmed that such viscosity increase may have originated from the intramolecular cyclization of forming oxazolidone structure, as illustrated in Scheme I. It was discovered that thermally aging or annealing the resin would effectively promote such structural transformation process from linear urethane to cyclic urethane without any involvement of the (meth)acrylate groups. In addition, it was further discovered that the very same structural transformation process could also be effectively achieved in presence of acidic catalysts. For example, trace amounts of inorganic or organic acid was able to effectively accelerate such transformation process (see Fig. 2). As used herein "trace amounts" refers to from about 0.01 weight percent to about 5 weight percent of the resin composition, such as from about 0.01 weight percent to about 3 weight percent or from about 0.05 weight percent to about 1.8 weight percent of the resin composition.

[0013] An inorganic acid could be a hydrochloric acid, hydrobromic acid, hydrofluoric acid, perchloric acid sulphuric acid, nitric acid, nitrous acid, phosphoric acid, carbonic acid, or the like.

[0014] An organic acid is an organic compound with acidic properties. The most common organic acids are the carboxylic acids, associating with their carboxyl group -COOH, sulfonic acids, containing the group -SO2OH, are relatively stronger acids. Some alcohols, with -OH, can also act as organic acids but they are usually very weak. Other groups can also confer acidity, such as compounds having the thiol group -SH, the enol group, and the phenol group. Examples of such organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, stearic acid, acrylic acid, methacrylic acid, fatty acids, amino acids, keto acids, aromatic carboxylic acids, dicarboxylic acids, tricarboxylic acids, alpha hydroxy acids. Further, phenolic acid compounds may include phenol, bisphenol, capsaicin, chavibetol, cresols, eugenol, 4-nonylphenol, picric acid (trinitrophenol), and the like.

R is independently linear, branched, and cyclic alkyl alkylether, aryl(phenyl, naphthalene and their substituted) or heterocyclic rings(thiophene, pyridine, furan and their substituted), alkaryl or a combination thereof;

R' is C1-C18 of alkyl or alkylethers or cyclic alkyl or cyclic alkylethers; or aryl(phenyl, naphthalene and their substituted) or heterocyclic rings(thiophene, pyridine, furan and their substituted); R" is hydrogen, C1-C18 of alkyl or alkylethers or cyclic alkyl or cyclic alkylethers; or aromatic rings(phenyl, naphthalene and their substituted) or heterocyclic rings(thiophene, pyridine, furan and their substituted); and

R'" is hydrogen C1-C18 of alkyl or alkylethers or cyclic alkyl or cyclic alkylethers; or aromatic rings(phenyl, naphthalene and their substituted) or heterocyclic rings(thiophene, pyridine, furan and their substituted).


EXAMPLES


1. Thermal annealing process on a model compound



[0015] A non polymerizable urethane compound (HPN-HMDI-HPN, as shown in Scheme V) was prepared by reactung 2-hydroxy-2-methylpropiophone (HPN) and 1,6-hexane diisocyanate (HMDI) in presence of a tin catalyst in solution. This crystalline compound was characterized by FTIR, NMR and HPLC analysis. Then it was subjected to thermal annealing, that is, the sample was heated to a temperature of from about 130°C to about 140°C at a rate of about 10°C/min and kept isothermal for from about 25 to about 4000mins. Then the annealed sample was analyzed by FTIR (see Fig. 3a and 3b) and NMR (see Fig. 4a and 4b), respectively. There were substantial structural changes during the thermal treatment on this compound. Additional comprehensive structural analysis on the annealed compound suggested that the structural changes involved the transformation of the urethane linkage within this compound from a linear form to a cyclic corm. In other words, the two linear urethane linkages in HPN-HMDI-HPN were readily transformed into a cyclic urethane linkage or oxazolidone upon use of the thermally annealing process. Such a structure was further confirmed by HPLC analysis.




2. Acid-catalyzed transformation process for a polymerizable resin (Comparative)



[0016] A polymerizable urethane resin (IEM-HP-IEM, Scheme VI) was prepared by reacting 2-hydroxyl-4'-(2-hydroxyethoxy)-2-methylpropiophone(HP) and 2-isocynate-ethoxyl methacrylate (IEM) in the presence of a tin catalyst in solution. This crystalline compound was characterized by FTIR, NMR and HPLC analysis. Then this crystalline resin was mixed with small amount of acidic monomer, about 1 weight percent of the final resin composition, succinic acid mono(2-methacryloloxyethyl) ester (HEMAS) in solution for about 90 mins. Then the resulting liquid resin was analyzed by FTIR and NMR respectively. There was a substantial structural change during such a treatment of this compound. Additional comprehensive structural analysis on the liquid resin suggested that such a structural change involved a similar transformation from a linear form to a cyclic form. In addition, it was also discovered that the conventional linearurethane linkage that existed in resin remained intact, which means it does not participate in the linear to cyclic transformation in any way. Therefore we concluded such a structural transformation of a given urethane linkage is highly selective and it is strictly depends upon the intrinsic nature of the linear urethane linkage. We further identified the structural criteria is the α-substituted β-ketone moiety.




3. Thermal annealing process on polymerizable resins



[0017] As shown in Scheme VII through VIII, additional polymerizable resins containing methacrylate and/or vinyl group and the unique α-substituted β-hetone moiety in the resins were examined via thermal annealing and acid-catalyzed treatments. As showed in Fig. 1 and Fig. 2, not only temperature plays a critical role to drive these urethanes to achieve an effective intramolecular cyclization, that is forming oxazolidone, it was also discovered that a small amount of organic acid, such as methacrylic acid can accelerate such a transformation process as well, even methacrylic acid as residue in HEMA o r HPMA can have this effect. Indeed the role of an acidic monomer on oxazolidone formation was confirmed by the rapid increase in viscosity for thermally aged resin in the presence of a monomer resin containing phosphoric acid, dipentaerythritol pentaacrylate monophosphate (PENTA) (see Fig. 1 and Fig. 2).






4. Control Example



[0018] Other urethane-based polymerizable resins, such as UDMA, an adduct of TMDI and HPMA; or TPH resin, a urethane-modified BisGMA resin with HMDI, were further treated under similar conditions. For instance, a formulated TPH resin with a photoacid generator, UVI-6983 and a formulated SDR II resin with same amount of UVI-6983 were exposed UV-Vis light for induced acid and then they were thermally aged at about 37°C for two weeks. There was no viscosity change for the TPH resin system, whereas an initial drop in viscosity was found and then it climbed back again in SDR II resin system. This indicated no structural transformation occurred in TPH resin system.


Claims

1. A process, comprising:

reacting a diisocyanate and an α-hydroxy-β-ketone to form a linear condensate,

converting the linear condensate into a cyclic oxazolidone based resin or polymer,

wherein converting the linear condensate is induced by thermally annealing the linear condensate at a temperature of from 25°C to 150°C, wherein the linear condensate includes polymerizable groups that remain intact even after the linear condensate is converted into the cyclic oxazolidone based resin or polymer.


 
2. The process according to claim 1, wherein the α-hydroxy-β-ketone has a structure of

wherein R' is C1-C18 of alkyl or alkylethers or cyclic alkyl or cyclic alkylethers; or aromatic rings (phenyl, naphthalene and their substituted) or heterocyclic rings (thiophene, pyridine, furan and their substituted);

wherein R" is hydrogen, C1-C18 of alkyl or alkylethers or cyclic alkyl or cyclic alkylethers; or aromatic rings (phenyl, naphthalene and their substituted) or heterocyclic rings (thiophene, pyridine, furan and their substituted); and

wherein R'" is hydrogen, C1-C18 of alkyl or alkylethers or cyclic alkyl or cyclic alkylethers; or aromatic rings (phenyl, naphthalene and their substituted) or heterocyclic rings (thiophene, pyridine, furan and their substituted).


 
3. The process according to claim 2, wherein the α-hydroxy-β-ketone is











wherein n is from about 2 to about 5.
 
4. The process according to claim 1, wherein the linear condensate includes a linear urethane linkage.
 
5. The process according to claim 1, wherein the polymerizable groups are acrylate, methacrylate, vinyl or combinations thereof.
 


Ansprüche

1. Prozess, umfassend:
Umsetzen eines Diisocyanats und eines α-Hydroxy-β-ketons zur Bildung eines linearen Kondensats, Umwandeln des linearen Kondensats in ein zyklisches Harz oder Polymer auf Oxazolidonbasis, wobei das Umwandeln des linearen Kondensats durch thermisches Tempern des linearen Kondensats bei einer Temperatur von 25 °C bis 150 °C induziert wird, wobei das lineare Kondensat polymerisierbare Gruppen beinhaltet, die intakt bleiben, selbst nachdem das lineare Kondensat in das zyklische Harz oder Polymer auf Oxazolidonbasis umgewandelt wird.
 
2. Prozess nach Anspruch 1, wobei das α-Hydroxy-β-keton die folgende Struktur aufweist:

wobei R' C1-C18 von Alkyl oder Alkylethern oder zyklischem Alkyl oder zyklischen Alkylethern; oder aromatische Ringe (Phenyl, Naphtalin und ihre Substitute) oder heterozyklische Ringe (Thiophen, Pyridin, Furan und ihre Substitute) ist;
wobei R" Wasserstoff, C1-C18 von Alkyl oder Alkylethern oder zyklischem Alkyl oder zyklischen Alkylethern; oder aromatische Ringe (Phenyl, Naphtalin und ihre Substitute) oder heterozyklische Ringe (Thiophen, Pyridin, Furan und ihre Substitute) ist; und wobei R'" Wasserstoff, C1-C18 von Alkyl oder Alkylethern oder zyklischem Alkyl oder zyklischen Alkylethern; oder aromatische Ringe (Phenyl, Naphtalin und ihre Substitute) oder heterozyklische Ringe (Thiophen, Pyridin, Furan und ihre Substitute) ist.
 
3. Prozess nach Anspruch 2, wobei das α-Hydroxy-β-keton Folgendes ist:











wobei n zwischen etwa 2 und etwa 5 beträgt.
 
4. Prozess nach Anspruch 1, worin das lineare Kondensat eine lineare Urethanbindung beinhaltet.
 
5. Prozess nach Anspruch 1, wobei die polymerisierbaren Gruppen Acrylat, Methacrylat, Vinyl oder Kombinationen davon sind.
 


Revendications

1. Procédé, comprenant :
la réaction d'un diisocyanate et d'une α-hydroxy-β-cétone pour former un condensat linéaire, la conversion du condensat linéaire en une résine ou un polymère à base d'oxazolidone cyclique, dans lequel la conversion du condensat linéaire est induite par un recuit thermique du condensat linéaire à une température de 25 °C à 150 °C, dans lequel le condensat linéaire comporte des groupes polymérisables qui restent intacts, même après la conversion du condensat linéaire en résine ou polymère à base d'oxazolidone cyclique.
 
2. Procédé selon la revendication 1, dans lequel l'α-hydroxy-β-cétone a une structure de

où R' est un groupe alkyle en C1-C18 ou des alkyléthers ou un groupe alkyle cyclique des alkyléthers cycliques ; ou des cycles aromatiques (phényle, naphtalène et leurs substituants) ou des cycles hétérocycliques (thiophène, pyridine, furane et leurs substituants) ;

où R" est un atome d'hydrogène, un groupe alkyle en C1-C18 ou des alkyléthers ou un groupe alkyle cyclique ou des alkyléthers cycliques ; ou des cycles aromatiques (phényle, naphtalène et leurs substituants) ou des cycles hétérocycliques (thiophène, pyridine, furane et leurs substituants) ; et

où R'" est un atome d'hydrogène, un groupe alkyle en C1-C18 ou des alkyléthers ou un groupe alkyle cyclique ou des alkyléthers cycliques ; ou des cycles aromatiques (phényle, naphtalène et leurs substituants) ou des cycles hétérocycliques (thiophène, pyridine, furane et leurs substituants).


 
3. Procédé selon la revendication 2, dans lequel l'α-hydroxy-β-cétone est











où n vaut environ 2 à environ 5.
 
4. Procédé selon la revendication 1, dans lequel le condensat linéaire comporte une liaison uréthane linéaire.
 
5. Procédé selon la revendication 1, dans lequel les groupes polymérisables sont acrylate, méthacrylate, vinyle ou leurs combinaisons.
 




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