ES2377614B1 - PROCEDURE FOR OBTAINING VINYL CO-NETWORKS BY SEQUENTIAL POLYMERIZATION. - Google Patents

Abstract

Method of obtaining vinyl co-networks by sequential polymerization. # The present invention relates to a method of obtaining vinyl co-networks by sequential polymerization, to the co-networks obtained by said process with a high conversion and at mild temperatures, and the uses of said co-networks as membranes for solute transport, sensor supports or catalysis.

Description

PROCESS FOR OBTAINING VINYL CO-NETWORKS BY SEQUENTIAL POLYMERIZATION

The present invention relates to a process for obtaining vinyl cores by sequential polymerization, to the co-networks obtained by said process, and the uses of co-networks as special membranes such as contact lenses, membranes for solute transport, supports for sensors or catalysis.

STATE OF THE PREVIOUS TECHNIQUE

Co-networks are two-component networks (also called "conetworks"), that is, chains of two types of polymer (polyA and polyB) interconnected with each other (as described in the article by Erdodi and Kennedy, Prog. Polym. Sci. 2006, 31, 1–18). It is a particular network topology, very different from that of a network of statistical copolymers in which poly (A-co-B) copolymer chains are connected, and in a certain sense alternative to the interpenetrated network (IPN). These differences give it special properties and characteristics, in regard to, for example, mechanical performance. On the other hand, if the two types of polymer chains are incompatible, as for example in the known amphiphilic co-networks mentioned in the work of Erdodi et al, under suitable conditions 2 co-continuous phases can be obtained. The two components of the co-networks can segregate into nano dimensions as chemical connectivities confine the phases to this scale.

This type of morphology, of great relevance, has revolutionized, among others, the area of contact lenses because the co-continuity of the phases has allowed to prepare materials that simultaneously allow hydration and comfort of the eye (associated with the hydrophilic phase ) and the appropriate passage of oxygen (associated with the hydrophobic silicone phase). On the other hand, the very high interfacial area added to co-continuity makes them very attractive in catalysis as mentioned in N. Bruns, J.C. Tiller, Nano Lett., 2005, 5, 45-48. In addition, nanostructured systems that are useful in many areas such as sensor preparation can be obtained

(M. Hanko, et Al, Anal. Chem. 2006, 78, 6376-6383).

The co-networks described in the state of the art have been prepared by using, as precursors, polymer blocks - of at least one of the components - functionalized at the chain ends.

DESCRIPTION OF THE INVENTION

The present invention provides a process for obtaining vinyl polymeric co-networks by sequential polymerization, to the cores obtained by said process, and to the uses of the co-networks as special membranes such as contact lenses, solute transport, supports for sensors or catalysis.

In comparison with the procedures described in the prior art for the synthesis of co-networks, in the present invention an alternative method is proposed which is characterized by the simplicity of obtaining co-networks (see Scheme 1) by combining sequential polymerization and of little demanding and orthogonal couplings with respect to the polymerizable group.

A first aspect of the present invention relates to a process for obtaining vinyl polymeric co-networks (from now on the process of the invention) at temperatures between 20 and 100 ° C comprising the steps:

a) formation of a copolymer by radical copolymerization from a monomer A and a monomer of formula M1-F1, where M1 is a polymerizable vinyl moiety, and F1 is a functional precursor group of the entrapment.

b) coupling of a monomer of formula M2-F2, through the group F2 with the functionality F1 of the polymer obtained in step 5 (a), where M2 is a vinyl moiety equal to or different from M1, and

F2 a cross-linking precursor functional group, and

c) radical polymerization of the product obtained in step (b) with a B monomer.

Vinyl polymers are polymers obtained from vinyl monomers; that is, small molecules containing double carbon-carbon bonds.

The process of the invention results in co-networks in which the cross-linking points are side chain, unlike the chain end points described in the prior art. The co-networks described in the

The present invention presents a statistical distribution of said cross-linking points along the chains.

Scheme 1: Synthesis route of a polymeric co-network. Where A and B are 20 the main monomer units of the two-component system, and M1 and M2 are the polymerizable vinyl moieties conjugated to the F1 and F2 functionalities. Where F1 reacts with F2 to give E, as can be seen in some examples in Table 1.

In step (a), component A is copolymerized with an M1-F1 monomer carrying a crosslinker precursor functionality. Once the statistical copolymer (copolymer 1) is formed, the precursor group is converted in step (b) into a polymerizable group M2 by means of the F1-F2 coupling, obtaining multifunctional chains or side chain macromonomers in which the functionality load is control compositionally. In step (c) these multifunctional chains will be copolymerized with monomer B to obtain the pure co-network.

In a preferred embodiment, the solvent used is selected from the list comprising: dioxane, methanol, ethanol, isopropanol, dimethylformamide (DMF) and any combination thereof.

In a preferred embodiment the molar ratio between monomers A and M1-F1 is between 1000: 1 and 2: 1. In a more preferred embodiment the molar ratio between monomers A and M1-F1 is between 100: 1 and 10: 1

In a preferred embodiment the molar ratio between monomers B and M2-F2 is between 1000: 1 and 2: 1. In a more preferred embodiment the molar ratio between monomers B and M2-F2 is between 100: 1 and 10: 1.

In another preferred embodiment the ratio between monomer A and monomer B is between 5: 1 to 1: 5.

Preferably A and / or B is a vinyl monomer. More preferably, the vinyl monomer is selected from acrylic, styrenic, vinylpyrrolidone derivative or any combination thereof.

A and M1 can be the same polymerizable moiety. And independently B and M2 can in turn be the same polymerizable moiety.

In a preferred embodiment the cross-linking precursor functional group F1 and / or F2 is selected from: primary amine, secondary amine, alcohol, O-succinimide, acid anhydride, acid chloride, isocyanate, azide, alkyne or any combination thereof .

5 The table shows F1 / F2 couplings that meet the requirements of: simple, preferably with a conversion greater than 95%, more preferably greater than 99%, that do not require drastic conditions of preparation, solvent or temperature (between 0 and 60 ° C ) and are orthogonal with respect to polymerizable vinyl groups.

Coupling F1-F2 (or F2-F1) a

Secondary primary amine / O-succinimide (room temperature 2040 ° C)

M1 NH2 M2 O NO O + M1 NH M2

Primary-secondary amine / acid anhydride (low temperature 0-20 ° C) at

Primary-secondary amine or alcohol / acid chloride (low temperature 0-20ºC) b

Primary-secondary amine or alcohol / isocyanate (low temperature 0-20ºC) b

Click chemistry (room temperature 2040ºC)

M1 N3 M2 + M2 M1 N N N

Table 1. Notes: a) Couplings can go both ways. For example, the same cross-linking can be reached 1) by copolymerizing the ethylamine methacrylate in the first step and derivatizing with the succinimide acrylate in the second step, or 2) the succinimide acrylate can be copolymerized in the first stage and derivatized with ethyl methacrylate Amina in the second. b) R = H (primary amine), or R = alkyls or aryls (secondary amine).

In a more preferred embodiment, the primary or secondary amine is selected from: ethylamine methacrylate, propylamine methacrylamide, vinylaniline, vinylpyrrolidone derivative or any combination thereof.

In a more preferred embodiment, the alcohol is selected from 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 3-acryloylamino-1-propane, Nacrylolamido-ethoxyethanol, caprolactone 2- (methacryloxy) , poly (ethylene glycol) acrylate, poly (propylene glycol) methacrylate, polyethylene glycol) acrylate or alcohol derived from vinyl pyrrolidone.

In a more preferred embodiment, the isocyanate is ethyl isocyanate methacrylate.

In a more preferred embodiment, the O-succinimide is selected from acryloylsuccinimide or methacryloysuccinimide.

In a more preferred embodiment, the acid chloride is selected from acrylic acid chloride, methacrylic acid chloride or vinylpyrrolidone-derived acid chloride.

In a more preferred embodiment, the azide is propylazide methacrylate.

In another more preferred embodiment, the alkyne is selected from the alkyl derivative of vinyl pyrrolidone or propargyl methacrylate.

Preferably, the process of the invention further comprises the use of a polymerization reaction initiator of step (a) that is selected from the list comprising: azo bisisobutyro nitrile (AIBN), benzoyl peroxide, and other known thermal initiators by an expert in the field.

In a preferred embodiment, the polymerization is carried out in an inert atmosphere with no oxygen. In a more preferred embodiment, the atmosphere is nitrogen.

In another preferred embodiment, the polymerization can be carried out using photoinitiation and photoinitiators known to any person skilled in the art.

In another preferred embodiment the polymerization can be carried out using redox initiation and pairs of redox initiators known to any person skilled in the art

A second aspect of the present invention relates to a vinyl polymeric co-network obtainable by the process of the invention.

Based on the nature of the described monomers, components A and B for which co-networks with appropriate cross-linking can be formed would be: acrylics in general (such as the co-network described in the example of the invention), styrenics, or vinyl pyrrolidone derivatives (and any combination thereof).

In a preferred embodiment, the networks that make up the co-network are poly (methyl methacrylate) and poly (N-isopropylacrylamide).

In a preferred embodiment, the networks that make up the co-network are poly (butyl methacrylate) and poly (N, N-dimethylacrylamide).

In a preferred embodiment, the networks that make up the co-network are poly (methyl methacrylate) and poly (styrene).

In another preferred embodiment, the networks that make up the co-network are poly (styrene) and poly (vinyl pyrrolidone).

In another preferred embodiment, the networks that make up the co-network are poly (methyl methacrylate) and poly (vinyl pyrrolidone).

In another preferred embodiment, the networks that make up the co-network are poly (butyl methacrylate) and poly (vinyl pyrrolidone).

In a third aspect, the present invention relates to the use of the vinyl polymeric co-network as described above as membranes, preferably the membranes are selected from contact lenses, catalyst supports, sensors or transport membranes.

Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and drawings are provided by way of illustration, and are not intended to be limiting of the present invention.

DESCRIPTION OF THE FIGURES

Fig. 1. Shows the degree of swelling versus temperature for the ‘isomeric systems’ CR1 and RE1.

Fig. 2. Shows the degree of swelling versus temperature for the CR1, CR2, RMMA and RNIPA systems.

Fig. 3. Shows the proton NMR spectra of copolymers 1 (above) and 2 (below).

Fig. 4. Shows the ATR spectra of the 5 prepared networks.

EXAMPLES

The invention will now be illustrated by tests carried out by the inventors, which demonstrates the specificity and effectiveness of the process for obtaining vinyl co-networks.

5 An example of the simple amine / succinimide coupling has been successfully developed, which requires very mild conditions (temperatures between 20 and 40 ° C and using commercial monomers, to obtain co-nets polymethyl methacrylate / poly (N- isopropylacrylamide), (PMMA-PNIPA) using simple chemistry and couplings

10 amine / succinimide. In the design of the synthetic procedure (scheme 2, shown below), the structural homology between the two types of polymerizable functions, methacrylate (MMA and ethylamine methacrylate) and acrylamide (in NIPA and in copolymer 2), have been preserved. thus optimizing cross-linking homogeneity.

15 In the synthetic procedure followed in scheme 2, the structural homology between the two types of polymerizable functions, methacrylate (MMA and ethylamine methacrylate) and acrylamide (in NIPA and in monomer 2) has been preserved, thus optimizing cross-linking homogeneity .

Scheme 2. Synthetic scheme used in the present example. Where AIBN is Azo bis-isobutyro nitrile, NIPAm is N-Isopropylacrylamide, RT is 5 room temperature and TEA is triethylamine.

Two CR1 and CR2 co-networks have been prepared, one equimolar and one with a NIPA / MMA molar ratio of 2: 1. To carry out a comparative analysis, RMMA and RNIPA reference networks of a component have also been prepared and the statistical network RE1 ‘isomeric’ of CR1 obtained

10 by simultaneous copolymerization of MMA and NIPA. Table 2 shows the data of these networks.

Label

Formulation VPTT (ºC) a)

CR1 (Co-red 1-1)

Copolymer 2 + NIPA (MMA-NIPA 1: 1 molar ratio) 29

CR2 (Co-network 1-2)

Copolymer 2+ NIPA + bisb) (MMA-NIPA 1: 2 molar ratio) 31

RE1 (MMA-NIPA Network)

MMA + NIPA + 5% of bis (MMA-NIPA 1: 1 molar ratio) 17

RMMA (MMAred)

MMA + 5% of EGDMA -

RNIPA (NIPAred)

NIPA + 5% of bis 32

Table 2. Feed compositions used to prepare the different networks and co-networks. Being EGDMA ethylene glycol dimethacrylate and bis bisacrylamide.

5 a) VPTT = volume phase transition temperature. It is the corresponding transition to LCST networks (lower critical solution temperature) used in soluble linear chains. VPTT can be defined as the temperature at which the hydrogel shows a 20% increase in swelling compared to the baseline, being

10 this one over the transition. Figure 1 shows the degree of swelling versus temperature for the ‘isomeric systems’ CR1 and RE1.

b) In the case of the CR2 network, the necessary amount of bis (2.5% molar with respect to the total monomers) has been added to reach a theoretical degree of cross-linking of 5%.

The co-networks obtained have shown a very particular thermosensitivity (associated with the NIPA thermosensitive component), very different from the conventional statistical networks obtained by simultaneous copolymerization of the two components, as shown in Figure 1.

20 Both systems have the same number of MMA and NIPA units (they can be considered ‘isomeric’ from this point of view), but nevertheless the topology is completely different, as well as the thermosensitivity.

These ‘in vitro’ data have been obtained gravimetrically as a function of temperature (5-50 ºC) after immersing the samples in distilled water. The samples have been allowed to equilibrate 1 day at each temperature before taking a measurement. This was carried out by carefully removing non-absorbed water using filter paper. The degree of swelling has been determined using the expression:

W - W

t 0

Degree of swelling (S,%) = × 100, where Wt and W0 are the weights W0

of swollen and dried samples respectively.

The co-network shows a VPTT 10 degrees higher than the statistical network obtained by simultaneous copolymerization (29 and 17 ° C respectively). The maximum swelling below the VPTT is very similar. Figure 2 comparatively shows the swelling vs. temperature graphs for the reference networks of an RMMA and RNIPA component and for the CR2 network with a NIPA / MMA molar ratio of 2: 1. The results indicate that swelling below the transition seems to be controlled by the compositional average, while the transition temperature is related to the topology. This unique behavior illustrates the possibilities of this approach to obtain unpublished topologies and networks with particular properties.

The strategy used successfully for the MMA / NIPA couple can easily be extended to other couples of interest with generic acrylic, styrenic components, or vinyl pyrrolidone derivatives.

Experimental preparation and study of PMMA / PNIPA co-networks

The copolymers and the networks of Table 2 were prepared by conventional radical polymerization, in dioxane, at 60 ° C for 24 h and using 2,2′-azobisisobutyronitrile (AIBN) as initiator. For the preparation of copolymer 1 methanol was used. The reactions were carried out in the absence of oxygen, which was displaced by bubbling N2 for 40 minutes before closing the system. The monomer and initiator concentrations were 2 and 0.015 mol / l respectively. In the case of the networks, the molar content of crosslinker was 5% with respect to the monomers. Copolymer 1 was precipitated and washed with water, and dried under vacuum until constant weighing in a glass desiccator.

To synthesize copolymer 2, copolymer 1 was solubilized in chloroform at room temperature. An equimolar amount of acryloyl succinimide and an excess of triethylamine were added under flow of N2. The reaction mixture was kept at room temperature overnight. Copolymer 2 was isolated by precipitation and washing in ethyl ether, followed by drying under vacuum until constant weighing. The proton spectra of copolymers 1 and 2 are shown in Figure 3. The incorporation of the two methacrylates in the copolymer and the acrylamide functionalization in copolymer 2 are observed. The integrals were consistent with the nominal percentage of 5%. cool.

Stage c was carried out in a glass container; Co-networks CR1 and CR2 were isolated by breaking the glass container. Then they were thoroughly washed with dioxane. The samples for ATR (attenuated total reflectance) were frozen and lyophilized. The samples for the thermosensitivity studies were transferred to water by a gradual change of dioxane medium to water at room temperature.

The reference networks RE1, RMMA and RNIPA were prepared, the last two being the reference networks of a component. The RE1 network is an "isomeric" system to the CR1, that is, with the same nominal amount of the two monomer units, but without co-network topology as they are cross-linked statistical copolymer chains, obtained by simultaneous copolymerization in the presence of bisacrylamide.

All prepared networks were analyzed by FTIR (Fourier Transform Infrared Spectrophotometer) using a Perkin-Elmer Spectrum One coupled to an ATR device. For each spectrum, 4 scans were recorded with a resolution of 4 cm-1 (Figure 4). It is interesting to analyze comparatively the spectra of the co-network CR1 and the ‘isomeric network’ RE1 (obtained by simultaneous copolymerization in the presence of bisacrylamide). Both spectra are equal, which is in accordance with the ‘isomerism’, that is, the equimolarity present in both systems. The CR2 co-network is obviously richer in NIPA.

Claims (32)

1. Procedure for obtaining vinyl polymeric co-networks at temperatures between 20 and 100 ° C comprising the steps:

to.

formation of a copolymer by radical polymerization from a monomer A and a monomer of formula M1-F1, where M1 is a polymerizable vinyl moiety, and F1 is a cross-linking precursor functional group,

b.

coupling of a monomer of formula M2-F2, through the group F2 with the functionality F1 of the polymer obtained in step (a), where M2 is a vinyl moiety equal to or different from M1, and F2 is a functional cross-linking precursor group , Y

C.

radical polymerization of the product obtained in step (b) with a B monomer.

2.

Process according to claim 1, wherein the solvent used is selected from the list comprising: dioxane, methanol, ethanol, isopropanol, dimethylformamide and any combination thereof.

3.

Process according to any one of claims 1 or 2, wherein the molar ratio between monomers A and M1-F1 is between 1000: 1 and the

2: 1.

Four.

Method according to claim 3, wherein the molar ratio between monomers A and M1-F1 is between 100: 1 and 10: 1.

5.

Process according to any one of claims 1 to 4, wherein the molar ratio between monomers B and M2-F2 is between 1000: 1 and the

2: 1.

6.

Method according to any one of claim 5, wherein the molar ratio between monomers B and M2-F2 is between 100: 1 and 10: 1.

7.

Process according to any one of claims 1 to 6, wherein the ratio between monomer A and monomer B is between 5: 1 to 1: 5.

8.

Process according to any one of claims 1 to 7, wherein A and / or B are vinyl monomers.

9.

Process according to claim 8, wherein the vinyl monomers are selected from acrylic, styrenic, vinylpyrrolidone derivative or any combination thereof.

10. Procedure according to any of claims 1 to 9, wherein A and M1 are the same polymerizable moiety. 11. Procedure according to any of claims 1 to 10, wherein B and M2 are the same polymerizable moiety. 12. Procedure according to any of claims 1 to 11, wherein the cross-linking precursor functional group F1 and / or F2 is selected from: primary amine, secondary amine, alcohol, O-succinamide, acid anhydride, acid chloride, isocyanate , azide, alkyne or any combination thereof. 13. The method according to claim 12, wherein the primary or secondary amine is selected from: ethylamine methacrylate, propylamine methacrylamide, vinylaniline, vinylpyrrolidone derivative or any combination thereof. 14. The method according to claim 12, wherein the alcohol is selected from 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 3-acryloylamino-1-propane, N-acrylolamido-ethoxyethanol, caprolactone 2 ( methacryloxy) ethyl ester, poly (ethylene glycol) acrylate, poly (propylene glycol) methacrylate, polyethylene glycol) acrylate or alcohol derived from vinyl pyrrolidone. 15. The method according to claim 12, wherein the isocyanate is ethyl isocyanate methacrylate. 16. The method according to claim 12, wherein the O-succinimide is selected from acryloylsuccinimide or methacryloysuccinimide. 17. The method according to claim 12, wherein the acid chloride is selected from acrylic acid chloride, methacrylic acid chloride or vinylpyrrolidone-derived acid chloride. 18. The method of claim 12, wherein the azide is propyl azide methacrylate. 19. The method according to claim 12, wherein the alkyne is selected from the alkyl derivative of vinyl pyrrolidone or propargyl methacrylate. 20. Procedure according to any one of claims 1 to 19, wherein it further comprises the use of a polymerization reaction initiator of step (a) that is selected from the list comprising: azo bisisobutyro nitrile and benzoyl peroxide. 21. Procedure according to any of claims 1 to 20, wherein the polymerization is carried out in an inert atmosphere. 22. Procedure according to claim 21, wherein the atmosphere is nitrogen. 23. Procedure according to any one of claims 1 to 22, wherein the polymerization is carried out using photoinitiation and photoinitiators known to a person skilled in the art 24.Procedure according to any of claims 1 to 23, wherein the polymerization is carried out using redox initiation and pairs of redox initiators known to a person skilled in the art 25. Vinyl polymeric co-network obtainable according to any of claims 1 to 24. 26. The co-network according to claim 25, wherein the networks composing the wall are poly (methyl methacrylate) and poly (N-isopropylacrylamide). 27. The co-network according to claim 25, wherein the networks comprising the wall are poly (butyl methacrylate) and poly (N, N-dimethylacrylamide). 28. Co-network according to claim 25, wherein the networks that make up the wall are poly (methyl methacrylate) and poly (styrene). 29. Co-network according to claim 25, wherein the networks comprising the co10 network are poly (styrene) and poly (vinyl pyrrolidone). 30. The co-network according to claim 25, wherein the networks comprising the wall are poly (methyl methacrylate) and poly (vinyl pyrrolidone). 31. The co-network according to claim 25, wherein the networks comprising the wall are poly (butyl methacrylate) and poly (vinyl pyrrolidone). 32. Use of the vinyl polymeric co-network according to any of claims 25 to 31, as membranes. 33. Use according to claim 32. wherein the membranes are selected from contact lenses, catalyst holders, sensors or transport membranes. SPANISH OFFICE OF THE PATENTS AND BRAND Application no .: 201030764 SPAIN Date of submission of the application: 05.20.2010 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: C08F265 / 06 (2006.01) C08G63 / 52 (2006.01) RELEVANT DOCUMENTS

Category

56 Documents cited Claims Affected

X

D. DEMIRGÖZ et al., “Asymmetric bihomologous crosslinkers for bicomponent gels-The way to 1-12,14,24,25,

strongly increased elastic moduli ”, Journal of Applied Polymer Science, 2010 [accessible online 15.09.2009], vol. 115, no. 2, pages 896-900.

26.27

X

H. REINECKE et al., "Symmetric versus asymmetric" homologous "vinylic cross-linkers in twocomponents networks: Formation of pseudo-conetworks or pseudo-IPNs", Macromolecular Theory and Simulations, 2009, vol. 18, no. 1, pages 25-29. 1,8,9,10,11.25

X

J. ZHANG et al., "Synthesis and characterization of pHand temperature-sensitive 1-12,14,21-23,

poly (methacrylic acid) / poly (N-isopropylacrylamide) interpenetrating polymeric networks ”, Macromolecules, 2000, vol. 33, no. 1, pages 102-107.

25.26.32.33

TO

M. VAMVAKAKI et al., "Synthesis and caharacterization of the swelling and nechanical properties of amphiphilic ionizable model co-networks containing n-butyl methacrylate hydrophobic blocks", Soft Matter, 2008, vol. 4, no. 2, pages 268-276. 1-33

TO

J-H JUNG et al., "Synthesis and physical properties of stimuli-sensitive copolymeric hydrogels (I): Hydrophilic-hydrophobic poly (N-isopropylacrylamide) copolymer systems", Korea Polymer Journal, 1994, vol. 2, no. 2, pages 85-90. 1-33

TO

WO 2009058397 A1 (THE UNIVERSITY OF AKRON) 07.05.2009, the whole document. 1-33

TO

US 2008/0051513 A1 (J. P. KENNEDY et al.) 28.02.2008, the whole document. 1-33

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims • for claims no:

Date of realization of the report 14.03.2012

Examiner E. Dávila Muro Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 201030764 Minimum documentation sought (classification system followed by classification symbols) C08F, C08G Electronic databases consulted during the search (name of the database and, if possible, terms of search used) INVENES, EPODOC, WPI, XPESP, CAPLUS, BIOSIS, MEDLINE State of the Art Report Page 2/4  WRITTEN OPINION Application number: 201030764 Date of the Written Opinion: 14.03.2012 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims Claims 13.15-20.28-31 1-12.14.21-27.32.33 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims Claims 1-33 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 201030764 1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

D. DEMIRGÖZ et al., Journal of Applied Polymer Science, 2010, vol. 115, nº 2, pp. 896-900

D02

H. REINECKE et al., Macromolecular Theory and Simulations, 2009, vol. 18, No. 1, pp. 25-29

D03

J. ZHANG et al., Macromolecules, 2000, vol. 33, No. 1, pp. 102-107

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The invention relates to a process for obtaining vinyl polymeric co-networks by means of radical sequential polymerization. It also refers to the co-networks obtained by said procedure and their use as membranes for solute transport, supports for catalysts, sensors and contact lenses. Document D01 discloses a process for obtaining vinyl co-networks by radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) and acrylamide (AA) monomers in ethanol in the presence of 5% of the symmetrical crosslinker ethylene glycol dimethacrylate (EGDMA), and bisacrylamide (EGDMA) monomers BIS) and the asymmetric acrylamide ethylene methacrylate (METAA); Sodium persulfate and vitamin C are used as redox initiators. The document indicates that using symmetric crosslinkers the system tends to form IPN interpenetrated networks while with asymmetric crosslinkers it tends to form vinyl co-networks (see pages 897 and 900). Document D02 is similar to the previous one and discloses the radical copolymerization of heterogeneous hydroxyethyl methacrylate and acrylamide monomers crosslinked with "monohomologists" symmetric monomers (EGDMA, BIS, DVB) and "bihomologists" asymmetric monomers (to obtain interpenetrated or AApe nets) - Vinyl networks. Document D03 discloses the obtaining of vinyl polymeric networks of poly-N-isopropylacrylamide (PNIPAAm) and polymethacrylic (PMAA) cross-linked with tetraethylene glycol dimethyl acrylate (TEGDMA) monomers by sequential polymerization by UV radiation in the presence of a 2,2-dimethoxy-2-dimethoxy photoinitiator -phenylacetophenone. The hydrogels thus obtained are used as drug transport membranes. Accordingly, the object of the invention set forth in claims 1-12,14,21-27,32,33 is already known in view of documents D01-D03. Therefore, these claims are not considered new or inventive according to articles 6.1 and 8.1 LP 11/1986. With respect to claims 13,15-20,28-31, although it has not been found in the state of the art to obtain vinyl polymeric cores using a cross-linking monomer with amine, isocyanate, succinimide, acid chloride, azide or functional groups. alkyne, or processes that give rise to polymeric co-networks of poly (meth) acrylate with polystyrene or polyvinylpyrrolidone, is considered within the scope of the usual practice followed by the person skilled in the art, especially since the advantages achieved are easily anticipated, as is the fact of obtaining polymeric co-networks formed by chains of two types of vinyl polymers interconnected with each other. Accordingly, claims 13.15-20.28-31 lack inventive activity according to article 8.1 LP 11/1986. State of the Art Report Page 4/4