Composition for producing a polymer, a method for producing the polymer, said polymer, use of the polymer, and an electrically dimmable glazing enclosing the polymer

Abstract

The present invention relates to a composition for producing a polymer, comprising: a) from 20 to 60% by weight, based on the entire composition, of at least one monomer; and b) from 30 to 60% by weight, based on the entire composition, of at least one branched pre-polymer, wherein the composition is liquid at room temperature and under normal pressure; use of the composition, a method for producing a polymer using the composition, as well as an electrically dimmable glazing that encloses the polymer.

Claims

1. A composition for producing a polymer, comprising: 20 to 60% by weight, based on the entire composition, of at least one monomer; and 30 to 60% by weight, based on the entire composition, of at least one branched pre-polymer, wherein the composition is liquid at 20° C. and 1 bar; the at least one monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, methyl acrylate, ethyl acrylate, vinyl chloride, acrylonitrile, vinyl acetate, styrene, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, N-Isopropyl acrylamide, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, 2-vinylpyridine, 4-vinylpyridine, and any combination thereof; and the branched pre-polymer is a reaction product of a) at least one monomer having one polymerizable group, b) at least one monomer having at least two polymerizable groups, and c) at least one chain transfer agent.

2. The composition according to claim 1, wherein the at least one chain transfer agent includes an aliphatic thiol, an aromatic thiol, or a combination thereof.

3. The composition according to claim 1, wherein the branched pre-polymer has a number average of the molar mass M.sub.n of 1,000 to 10,000 g/mol.

4. The composition according to claim 1, wherein the branched pre-polymer has a weight average of the molar mass M.sub.w of 2,000 to 40,000 g/mol.

5. The composition according to claim 1, wherein the pre-polymer has a dispersity of 2 to 10.

6. The composition according to claim 5, wherein the branched pre-polymer has a dispersity of 2.5 to 8.

7. The composition of claim 1, wherein a viscosity of the composition is not greater than 41 mPas.

8. The composition according to claim 1, wherein the branched pre-polymer includes a branched poly(alkyl)acrylate, a branched polyacrylate, a branched polystyrene, or a combination thereof.

9. The composition according to claim 8, wherein the branched pre-polymer includes branched poly-n-butyl acrylate, branched poly-2-ethylhexyl acrylate, branched poly(n-butyl acrylate-co-2-ethylhexyl acrylate), or any combination thereof.

10. The composition according to claim 1, wherein the monomer of the composition includes n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, styrene, or any combination thereof.

11. The composition according to claim 1, wherein the composition comprises a further monomer having at least two polymerizable groups in an amount of 0.1 to 2% by weight based on the total weight of the composition.

12. The composition of claim 1, wherein the composition is adapted for producing a dental composite, a glass ionomer cement, an acrylate adhesive, an acrylic glass sheet, an acrylic material in electrical engineering, or a glass-polymer-glass composite pane.

13. An electrically dimmable glazing comprising the polymer of claim 1.

14. A method of producing a polymer, comprising: forming a branched pre-polymer, wherein forming the branched pre-polymer comprises reacting a) at least one monomer having one polymerizable group, b) at least one monomer having at least two polymerizable groups, and c) at least one chain transfer agent; preparing a composition comprising 30-60 wt % of the branched pre-polymer and 20-60 wt % of at least one monomer, the monomer being selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, methyl acrylate, ethyl acrylate, vinyl chloride, acrylonitrile, vinyl acetate, styrene, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, N-Isopropyl acryl; and reacting the composition to form the polymer.

15. The method of claim 14, wherein a shrinkage of the composition after reacting the composition and forming the polymer is not greater than 7%.

16. The method of claim 14, wherein a viscosity of the composition is not greater than 41 mPas.

17. The method of claim 14, wherein a ratio for forming the branched pre-polymer of a) the at least one monomer having one polymerizable group to b) the at least one monomer having at least two polymerizable groups to c) the at least one chain transfer agent is 1-100/1/0.1-10.

18. The method according to claim 14, wherein the branched pre-polymer includes a branched poly(alkyl)acrylate, a branched polyacrylate, a branched polystyrene, or a combination thereof.

Description

(1) FIG. 1: Difference in the viscosity increase of linear and branched polystyrene as a function of the molar mass; (L-PS=linearly polymerized polystyrene, HBPS=branched polymerized polystyrene)

(2) In summary, this invention has the following advantages: The volume shrinkage of a monomeric mixture during curing is significantly reduced.

(3) The viscosity of the resin mixture remains low and can thus be used and pumped on an industrial scale.

(4) The invention will be illustrated below in an exemplary manner with reference to specific examples. These examples are illustrative of the invention and do not limit the scope of the invention as recited.

EXEMPLARY EMBODIMENTS

(5) The following exemplary embodiments are mentioned.

(6) Examples 1-3: Preparation of a branched polyacrylate from a pure monomer, for example, n-butyl acrylate; preparation of a polymer film with the branched polyacrylate and the same monomeric acrylate

(7) Examples 4-6: Preparation of a branched polyacrylate from a pure monomer, for example, 2-ethylhexyl acrylate; preparation of a polymer film with the branched poly-2-ethylhexyl acrylate and another monomeric acrylate, for example n-butyl acrylate.

(8) Examples 7-9: Preparation of a branched polyacrylate from a pure monomer for example, n-butyl acrylate; preparation of a film with the branched poly(n-butyl acrylate) or poly(ethyl hexyl acrylate) and a mixture of different monomeric acrylates, for example, n-butyl acrylate, 2-ethyl hexyl acrylate, 2-hydroxy ethyl acrylate.

(9) Examples 10-11: Preparation of a branched acrylate copolymer from various monomers, e.g. n-butyl acrylate and 2-ethylhexyl acrylate; preparation of a film with the branched poly (n-butyl acrylate-co-2-ethyl hexyl acrylate) and another monomeric acrylate, for example n-butyl acrylate

(10) Examples 12-14: Preparation of a branched acrylate copolymer from various monomers, e.g. n-butyl acrylate and 2-ethylhexyl acrylate; preparation of a film with the branched poly(n-butyl acrylate-co-2-ethyl hexyl acrylate) and a mixture of different monomeric acrylates, for example, n-butyl acrylate, ethyl hexyl acrylate, 2-hydroxy ethyl acrylate.

(11) Meanings are always the same: nBA n-butylacrylate EHA 2-ethylhexylacrylat HEA hydroxyethyl acrylate BDDA butanediol diacrylate DDT dodecanethiol TPGDA tripropylene glycol diacrylate DVB divinyl benzene THF tetrahydrofuran

Example 1: Preparation of a Poly(n-Butyl Acrylate) (PnBA) Film

(12) The used branched PnBA was prepared as follows. 3 kg nBA were mixed with 117 g of tripropylene glycol diacrylate (TPGDA), 395 g of dodecanethiol (DDT), and 1.6 g of Irgacure 819. After 15 minutes of degassing/purging with argon, the mixture was irradiated for 20 minutes with a 100 W Hg UV lamp. The obtained branched polymer had a purity of 76% (nBA), a molecular weight distribution of M.sub.n=1500 g/mol; Mw=4000 g/mol and a dispersity of 2.51.

(13) For the preparation of an ion-conductive polymer film for use in an electrochromic element, a cast resin mixture of 29.05% nBA, 54.65% branched PnBA, 13.4% propylene carbonate, 1.50% lithium perchlorate (anhydride), 1% 1.4-Butane diol diacrylate and 0.4% Irgacure 819 was subsequently produced. This cast resin mixture had a viscosity of 9.6 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 4% could be determined. A similar mixture without addition of branched PnBA has a viscosity of 1.1 mPas and a shrinkage after complete curing of 11%.

Example 2: Preparation of a Poly(Ethyl Hexyl Acrylate) (PEHA) Film

(14) The used branched PEHA was prepared as follows. 10 g EHA was mixed with 6.7 g tripropylene glycol diacrylate (TPGDA), 22.9 g dodecanethiol (DDT) and 95 mg Irgacure 819. After 15 minutes of degassing with argon, the mixture was irradiated for 20 minutes with a 100 W Hg UV lamp. The obtained branched polymer had a purity of 85% (15% unreacted EHA) and a molecular weight distribution of Mn=7600 g/mol; Mw=23200 g/mol, and a dispersity of 3. The obtained branched polymer had a purity of 85% (15% unreacted EHA) and a molecular weight distribution of M.sub.n=7600 g/mol; M.sub.w=23200 g/mol, and a dispersity of 3.

(15) For the film preparation, a cast resin mixture of 49.4% EHA; 36.5% branched PEHA; 13.4% propylene carbonate, 0.3% butanediol diacrylate (BDDA), and 0.4% Irgacure 819 was subsequently produced. This cast resin mixture had a viscosity of 20 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 5% could be determined. A similar mixture without the addition of the branched PEHA has a viscosity of 2 mPas and a shrinkage after complete curing of 8%.

Example 3: Preparation of a Polystyrene (PS) Film

(16) The used branched PS was produced as follows. 100 g of styrene with 2 g divinyl benzene (DVB), 16.2 g dodecanethiol (DDT), and 67 mg Irgacure 819 was dissolved in 50 mL of THF. After 15 minutes of degassing with argon, the mixture was irradiated for 20 minutes with a 100 W Hg UV lamp. The obtained branched polymer had a purity of 85% (15% unreacted EHA) and a molecular weight distribution of Mn=7600 g/mol; Mw=23200 g/mol, and a dispersity of 3. The obtained branched polymer had a purity of 81% (19% unreacted styrene) and a molecular weight distribution of M.sub.n=3750 g/mol; M.sub.w=29000 g/mol, and a dispersity of 7.8.

(17) For the film preparation, a cast resin mixture of 35.9% styrene; 50% branched PS; 13.4% propylene carbonate, 0.3% divinyl benzene and 0.4% Irgacure 819 was subsequently produced. This cast resin mixture had a viscosity of 31 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 4% could be determined. A similar mixture without the addition of the branched PS has a viscosity of 2 mPas and a shrinkage after complete curing of 15%.

Example 4: Preparation of a Film from Mixtures

(18) For film preparation, a cast resin mixture of 49.4% nBA; 36.5% branched PEHA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced This cast resin mixture had a viscosity of 18 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 6% could be determined. A similar mixture without the addition of the branched PEHA has a viscosity of 1.1 mPas and a shrinkage after complete curing of 11%.

Example 5: Preparation of a Film from Mixtures

(19) For the film preparation, a cast resin mixture of 49.4% EHA; 36.5% branched PnBA; 13.4% propylene carbonate. 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 20 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 4% could be determined. A similar mixture without addition of branched PnBA has a viscosity of 2 mPas and a shrinkage after complete curing of 8%.

Example 6: Preparation of a Film from Mixtures

(20) For film preparation, a casting resin mixture of 35.9% 2-hydroxyethylacrylate (HEA); 50% branched PnBA; 13.4% propylene carbonate, 0.3% 1,4-butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 41 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 5% could be determined. A similar mixture without addition of branched PnBA has a viscosity of 6 mPas and a shrinkage after complete curing of 14%.

Example 7: Preparation of a Film from Mixtures

(21) For the film preparation, a casting mixture of 30% nBA; 20% EHA; 35.9% branched PEHA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 23 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 5% could be determined. A similar mixture without the addition of the branched PEHA has a viscosity of 1.8 mPas and a shrinkage after complete curing of 10%.

Example 8: Preparation of a Film from Mixtures

(22) For the film preparation, a casting resin mixture of 30% nBA; 20% EHA; 35.9% branched PnBA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 21 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 6% could be determined. A similar mixture without the addition of the branched PEHA has a viscosity of 1.3 mPas and a shrinkage after complete curing of 11%.

Example 9: Preparation of a Film from Mixtures

(23) For the film preparation, a casting resin mixture of 20% nBA; 20% EHA; 10% 2-hydroxyethyl acrylate (HEA); 35.9% branched PnBA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 32 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 7% could be determined. A similar mixture without addition of branched PnBA has a viscosity of 4.2 mPas and a shrinkage after complete curing of 13%.

Example 10: Preparation of a Film from Mixtures

(24) The used branched copolymer (PnBA-co-PEHA) was produced as follows. 10 g nBA was mixed with 4.38 g EHA, 3.9 g tripropylene glycol diacrylate (TPGDA), 1.32 g dodecanethiol (DDT), and 5.4 mg Irgacure 819. After 15 minutes of degassing with argon, the mixture was irradiated for 20 minutes with a 100 W Hg UV lamp. The obtained branched polymer had a purity of 85% (15% unreacted EHA) and a molecular weight distribution of Mn=7600 g/mol; Mw=23200 g/mol, and a dispersity of 3. The obtained branched polymer had a purity of 81% (19% unreacted nBA and EHA) and a molecular weight distribution of M.sub.n=2300 g/mol; M.sub.w=6000 g/mol and dispersity of 2.6.

(25) For the film preparation, a casting resin mixture of 50% 2-hydroxyethyl acrylate (HEA); 35.9% branched PnBA-co-PEHA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 24 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 7% could be determined. A similar mixture without addition of the branched PnBA-co-PEHA has a viscosity of 6 mPas and a shrinkage after complete curing of 14%.

Example 11: Preparation of a Film from Mixtures

(26) For the film preparation, a casting resin mixture of 50% nBA; 35.9% branched PnBA-co-PEHA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 19 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 6% could be determined. A similar mixture without addition of the branched PnBA-co-PEHA has a viscosity of 1.1 mPas and a shrinkage after complete curing of 11%.

Example 12: Preparation of a Film from Mixtures

(27) For the film preparation, a casting resin mixture of 30% nBA; 20% EHA; 35.9% branched PnBA-co-PEHA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 21 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 5% could be determined. A similar mixture without addition of the branched PnBA-co-PEHA has a viscosity of 1.8 mPas and a shrinkage after complete curing of 10%.

Example 13: Preparation of a Film from Mixtures

(28) For the film preparation, a casting resin mixture of 30% nBA; 20% EHA; 35.9% branched PEHA-co-PnBA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 27 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 6% could be determined. A similar mixture without addition of the branched PEHA-co-PnBA has a viscosity of 1.8 mPas and a shrinkage after complete curing of 10%.

Example 14: Preparation of a Film from Mixtures

(29) For the film preparation, a casting resin mixture of 20% nBA; 20% EHA; 10% 2-hydroxyethyl acrylate (HEA); 35.9% branched PEHA-co-PnBA; 13.4% propylene carbonate, 0.3% butanediol diacrylate, and 0.4% Irgacure 819 was produced. This cast resin mixture had a viscosity of 36 mPas. After curing the film for 30 min under UV irradiation, a shrinkage of 7% could be determined. A similar mixture without addition of the branched PEHA-co-PnBA has a viscosity of 4.2 mPas and a shrinkage after complete curing of 13%.

(30) The invention can be used in all radical polymerizations in which the shrinkage during curing is to be reduced or avoided: [1] S. Loshaek, T. G. Fox, J. Am. Chem. Soc. 1953, 75, 3544-3550. [2] F. S. Nichols, R. G. Flowers, Ind. Eng. Chem. 1950, 42, 292-295. [3] Versluis A., Douglas W. H., Cross M., S. R. L., J Dent Res 1996, 75, 871-878. [4] Bailey William J., E. Takeshi, Journal of Polymer Science: Polymer Symposium 1978, 64, 17-26. [5] N. O'Brien, A. McKee, D. C. Sherrington, A. T. Slark, A. Titterton, Polymer 2000, 41, 6027-6031. [6] S. B. Kharchenko, R. M. Kannan, J. J. Cernohous, Macromolecules 2003, 36, 399-406.

(31) The features disclosed in the specification and claims may be relevant to the realization of embodiments both individually and in any combination with each other.