(19)
(11)EP 3 377 566 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.04.2020 Bulletin 2020/18

(21)Application number: 16788671.2

(22)Date of filing:  27.10.2016
(51)International Patent Classification (IPC): 
C08J 9/00(2006.01)
C08J 9/08(2006.01)
C08J 9/02(2006.01)
(86)International application number:
PCT/EP2016/075921
(87)International publication number:
WO 2017/084852 (26.05.2017 Gazette  2017/21)

(54)

FORMULATION OF POLYMERIC MIXTURES FOR THE PRODUCTION OF CROSS-LINKED EXPANDED PVC FOAMS AND PROCESS FOR PRODUCING SAID FOAMS

FORMULIERUNG VON POLYMERMISCHUNGEN ZUR HERSTELLUNG VON VERNETZTEN EXPANDIERTEN PVC-SCHÄUMEN UND VERFAHREN ZUR HERSTELLUNG DIESER SCHÄUME

FORMULATION DE MÉLANGES POLYMÈRES POUR LA PRODUCTION DE MOUSSES DE PVC EXPANSÉES RÉTICULÉES ET PROCÉDÉ DE PRODUCTION DESDITES MOUSSES


(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: 16.11.2015 IT UB20155596

(43)Date of publication of application:
26.09.2018 Bulletin 2018/39

(73)Proprietor: Diab International AB
312 22 Laholm (SE)

(72)Inventors:
  • BRESSAN, Raffaela
    31046 Oderzo (TV) (IT)
  • NART, Fabiano
    32036 Sedico (BL) (IT)
  • RENON, Marco
    32021 Agordo (BL) (IT)
  • TORGERSSEN, Ulf
    31232 Laholm (SE)

(74)Representative: Martegani, Franco et al
Via Carlo Alberto 41
20900 Monza
20900 Monza (IT)


(56)References cited: : 
WO-A1-2014/106867
US-A1- 2007 200 266
WO-A1-2015/088431
US-A1- 2010 068 487
  
      
    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 present invention relates to a formulation of polymeric mixtures for the production of cross-linked expanded PVC foams. The same invention is also extended to the process used for producing said cross-linked expanded PVC foam.

    [0002] The field of the invention relates to that of cross-linked expanded PVC foams used for the production of expanded materials such as PVC panels and the like, adopted as a core in the field of composite materials.

    [0003] Cross-linked expanded PVC foams are traditionally prepared starting from a mixture comprising PVC, isocyanates with a cross-linking function, anhydrides destined for reacting with water and isocyanate for the formation of amides during the expansion and cross-linking phase, an expanding agent based on diazo-compounds for the formation of gas (azobisisobutyronitrile AZDN) and a nucleating and stabilizing agent, also based on diazo-compounds (azodicarbonamide ADC).

    [0004] In particular, in the field of the production of cross-linked PVC foams, traditional ADC exerts a nucleating function, providing an expanded material having small closed cells (diameter of 0.4-0.6 mm), which serve for conferring a homogeneous structure to the expanded product, and with good mechanical properties. ADC also has a stabilizing function, inhibiting decomposition reactions of PVC during the moulding process of said mixture in a press.

    [0005] The traditional mixtures described above, however, have the disadvantage of using diazo-compounds, such as ADC and AZDN, which are undesired as they are dangerous. ADC is in fact in the black list of REACH, as it is classified as being a Very High Concerned (VHC) substance. AZDN is, in turn, a material in powder form classified as being explosive and susceptible of releasing toxic substances.

    [0006] US 2007/200266 A1 relates to a method for producing a cross-linked PVC foam body from a starting mixture containing PVC, an isocyanate or polyisocianate, an organic anhydride and a chemical expanding agent.

    [0007] WO 2014/106867 A1 discloses a process for the production of rigid foamed objects, wherein organic diazocompounds are employed in the manufacturing of said objects. The document discloses for example a composition comprising PVC, PMDI and either a liquid modified phthalic anhydride with diazo compounds or a solid phthalic anhydride with sodium bicarbonate.

    [0008] The document WO2015/088431 discloses an injection moulded product and a formulation for the production of cross-linked PVC foams comprising PVC, isocyanates, anhydride and blowing agent.

    [0009] The document US 2010/068487 discloses Formulation for cellular, foamed-polymer product based on polyvinyl chloride.

    [0010] The main objective of the present invention is to provide a formulation of a polymeric mixture for the production of expanded PVC foams which, unlike traditional formulations, allows the desired stabilization, nucleation and expansion degree to be obtained, even in the absence of azo-derivatives.

    [0011] A further objective of the invention is to provide a process suitable for producing expanded PVC foams with the use of the above-mentioned formulation of a polymeric mixture.

    [0012] These and other objectives are achieved with the formulation of a polymeric mixture and the process of claims 1 and 6 respectively. Preferred embodiments of the invention are specified in the remaining claims.

    [0013] With respect to known formulations for the production of cross-linked PVC foams, the formulation according to the invention offers the advantage of obtaining the desired stabilization, nucleation and expansion degree to be obtained, even in the absence of azo-derivatives.

    [0014] Furthermore, with the use of anhydrides liquid at room temperature of the formulation of the invention, the advantage is obtained that, in the heating phase in the press, heat does not have to be provided for melting the traditional anhydrides in the solid state. In this way, the liquid anhydride and isocyanate are reacted, with the formation of the necessary quantities of CO2 for the expansion of the PVC foam, without removing the heat from the reaction environment for melting the starting PVC.

    [0015] The above reaction between anhydride and isocyanate advantageously allows a basic imide structure to be obtained, which, with the subsequent completion of the reactions, leads to a cross-linked structure which is formed around the PVC chains. In this way, a final structure is created, called "Inter Penetrating Network" (IPN), with the presence of a high imide structure, suitable for conferring higher thermal properties than the traditional properties, to the PVC foam.

    [0016] It has also been surprisingly found that, with the use of zeolites and sodium bicarbonate in the quantities according to the invention (less than 3% by weight), alone or combined with each other, the HCl formed by thermal effect in the reaction environment, coming from the PVC and responsible for the degradation of the same polymer, is sequestered and neutralized by these substances, thus generating an expanded product which is thermally stabilized and free of degradation defects.

    [0017] These and other objectives, advantages and characteristics appear evident from the following description of some preferred embodiments of the formulation and process of the invention, illustrated, for purely exemplificative and non-limiting purposes, in the figures of the enclosed drawings.

    [0018] In these:
    • figures 1 to 4 illustrate, by means of an optical microscope, the cellular structure of a cross-linked expanded PVC foam, according to the known art and according to three examples of the invention, respectively;
    • figure 5 illustrates the trend of the thermal conductivity values of the foams of the previous figures;
    • figure 6 illustrates the trend of the resin absorption values of the foams of figures 1 to 4;
    • figure 7 illustrates the graph of the trend of the Storage Modulus in the Dynamic Mechanical Analysis (DMA) as a function of the temperature, in the foams of figures 1 to 4;
    • figures 8 and 9 illustrate microscope magnifications of the porous structure, of a zeolite and sodium carbonate of the invention, respectively;
    • figures 10 and 11 schematically illustrate anucleation example of a nucleation agent with a non-porous surface and porous surface, respectively.


    [0019] The polymeric mixture of the invention for the production of cross-linked expanded PVC foams has the objective of providing an expanded material without diazo-compounds, characterized by the presence of closed cells having a diameter smaller than or equal to 0.6 mm, i.e. sufficiently small to confer a homogeneous structure to the expanded product, having a low thermal conductivity, a reduced resin absorption and a higher glass transition temperature.

    [0020] To enable the gas to generate a stable core, capable of forming closed cells having a small diameter, a certain energy threshold must be exceeded, which, for this reason, must be as low as possible. This energy threshold depends, in particular, on the critical radius of said core, which in turn depends on the interfacial tension between the gas bubbles and the polymeric mass. In the system of the polymeric mixture of the invention, which has become heterogeneous due to the presence of nucleating agents, the free energy ΔGet to be exceeded is expressed by the formula:

    wherein:

    ΔGet = heterogeneous free energy, i.e. in the presence of nucleating agents

    ΔGom = homogeneous free energy, i.e. in the absence of nucleating agents

    wherein ∂ is the wettability angle.



    [0021] Furthermore, as 0<f(∂)<1, in order to obtain a low ΔGet value, f(∂) must approach zero, i.e. the angle ∂ must be high. For this reason, according to the invention, materials characterized by having a porous surface are used as nucleating agents for the production of cross-linked expanded PVC foams.

    [0022] In this case, in fact, and as better illustrated in figures 10 and 11, the angle ∂1 formed between the tangent t1 at the surface of the gas bubble 1 and the corresponding wall 2 of the porous nucleation site 3, is greater than the angle ∂2 formed between the tangent t2 at the surface of the gas bubble 4 and the corresponding wall 5 of the non-porous nucleation site 6.

    [0023] Nucleating agents suitable for the purposes of the invention are, for example, the zeolite of figure 8, with pores ranging from 2-50 nm, and the sodium bicarbonate of figure 9, with pores of about 100 nm. The porosity of the nucleating agent for the purposes of the invention is 1-100 nm, more preferably 2-50 nm. Furthermore, the desired porosity degree of the sodium bicarbonate is advantageously obtained, according to the invention, in the hot pressing phase of the formation process of cross-linked PVC foams.

    [0024] According to the invention, the CO2 gas phase is given by the following reaction between isocyanate and anhydride:

    wherein

    R1 = C6H12; C9H18; C12H24; C10H18; C13H10; C6H4; C7H5; C10H6; C16H11; C7H6

    R2 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12.



    [0025] According to a preferred variant of the invention, the CO2 gas phase is given by the following reaction between isocyanate and anhydride:

    wherein:

    R1 = C6H4, C7H6

    R2 = C6H12; C9H18; C12H24; C10H18; C13H10; C6H4; C7H5; C10H6; C16H11; C7H6;

    R3 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12.



    [0026] As can be observed, in these reactions, use is no longer made of the traditional diazo-compounds, with the function of expanding agents for the production of N2.

    [0027] The zeolites suitable for the invention are of the aluminosilicate type:

            xMO • ySiO2 · zAl2O3

    wherein:

    x = 0 - 0.5

    y = 0 - 0.5

    z = 0.5 - 1

    M = Na, K, Ca, NH4, Fe.



    [0028] Furthermore, whereas the zeolites act exclusively as stabilizing and nucleating agents, the sodium bicarbonate of the invention also adds the effect of contributing to the cell expansion, producing CO2 through the following reaction with hydrochloric acid coming from PVC:

            NaHCO3+HCl→ NaCl + CO2 +H2O



    [0029] In order to not subtract heat from the PVC melting process, the quantities of bicarbonate used are advantageously and preferably lower than 3% by weight. Furthermore, again with the same objective, the anhydrides used are those that are in the liquid state at room temperature, in particular anhydrides having formula:

    wherein

    R3 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6;

    C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12.



    [0030] In this way, it is no longer necessary to have heat that serves for melting the traditional solid anhydrides. In addition, the use of the liquid anhydrides of the invention introduces imide structures into the reaction environment, necessary for the formation of an IPN-Inter Penetrating Network, having better thermal properties.

    [0031] The following formulations containing, by weight:
    PVC 30-60%
    Isocyanate 20-60%
    Liquid anhydrides 3-40%
    said formulations further comprising:
    Zeolites less than 3%
    Sodium bicarbonate less than 3%
    are preferred for the invention.

    [0032] In the table, the following formulations are compared:
    1. A formulations of the known art, in which diazo-derivatives are used, with both a nucleating and stabilizing function (ADC), and also with the function of blowing agent (AZDN) (Figure 1);
    2. B formulation of the invention, with sodium bicarbonate alone (Figure 2);
    3. C formulation of the invention, with sodium bicarbonate and zeolite (Figure 3);
    4. D formulation of the invention, with zeolite alone (Figure 4).


    [0033] The foams obtained with these formulations were tested with respect to thermal conductivity, which must be as low as possible, the resin absorption quantity, which must also have minimum values, and the glass transition temperature, preferably high. The results of these tests are indicated in the following table, in which the quantities of compounds in the mixture are expressed as weight percentages:
     ABCD
    PVC 40 40 40 40
    Isocyanate 51 51 51 51
    Anhydride Phthalic (solid) Hexahydrophthalic (liquid) Hexahydrophthalic (liquid) Hexahydrophthalic (liquid)
    5 8 8 8
    ADC 0.5 / / /
    AZDN 3.5 / / /
    Zeolite / / 0.5 3
    Sodiumbicarbonate / 2 2 /
    Cell diameter (mm) 0.52 0.41 0.3 0.08
    Thermal conductivity (W/m·°K) 0.031 0.03 0.029 0.026
    Resinabsorption (g/m2) 389 280 199 0
    Glass transition temperature Tg(°C) 91 101 105 109


    [0034] From this table, it can be observed that the cross-linked expanded PVC foams have closed cells with a diameter smaller than or equal to 0.6 mm, i.e. sufficiently small to confer a homogeneous structure to the expanded product, with a thermal conductivity lower than 0.030 W/m°K, a resin absorption lower than 300 g/m2 and a glass transition temperature higher than 100°C.

    [0035] The surface of the cross-linked expanded PVC foams of the previous table has the appearance illustrated in figures 1 to 4, in which a decrease in the cell diameter in the foams of the invention, can be observed. The best results are obtained with formulation D of figure 4, which comprises high quantities of zeolite.

    [0036] In the process of the invention, the polymeric mixture is prepared by first introducing the liquid components (isocyanate and anhydride) into the mixer, followed by the powders of porous stabilizing and nucleating agents, and finally PVC. The mixing is effected under vacuum for stripping the air and the mixture thus obtained is poured into moulds which are heated under pressure in a press (80-180 bar) to a temperature of 160-180°C for the time necessary for melting the PVC and for the isocyanate-anhydride cross-linking reactions and formation of the gas phase. It is during this hot compression that the sodium bicarbonate possibly present acquires the porous structure of the invention.

    [0037] The material obtained from the hot pressing, in which the cross-linking reactions between isocyanate and anhydride have partially taken place, and with the formation of imide and CO2, is then subjected to the expansion and cross-linking process in the presence of water vapour, at temperatures of 80-99°C and 45-70°C, respectively. In this phase, the water reacts with the remaining isocyanate and anhydride reagents, thus completing the cross-linking reactions and producing additional quantities of CO2. The cross-linked expanded PVC foams of the invention (known as "Inter Penetrating Network"-IPN)are thus obtained, whose properties in terms of thermal conductivity, resin absorption and glass transition temperature, with the same cell diameter, are higher with respect to the foams of the known art.


    Claims

    1. A formulation of polymeric mixtures for the production of cross-linked expanded PVC foams, of the type comprising PVC, isocyanates, anhydrides and one or more nucleating agents, characterized in that said anhydrides are liquid at the room temperature, in that said nucleating agents consist of porous nucleating materials and in the absence of diazocompounds, said nucleating agent consisting of porous zeolite, composed of aluminosilicates of the type:

            xMO • ySiO2 · zAl2O3

    wherein:

    x = 0 - 0.5

    y = 0 - 0.5

    z = 0.5 - 1

    M = Na, K, Ca, NH4, : Fe,

    or a combination of said zeolite with porous sodium bicarbonate.


     
    2. The formulation according to claim 1, characterized in that said nucleating agent comprises porous sodium bicarbonate.
     
    3. The formulation according to claim 2, characterized in that said porous sodium bicarbonate is present in the mixture in quantities lower than 3% by weight.
     
    4. The formulation according to claim 3, characterized in that said anhydrides have formula:

    wherein
    R3 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12.
     
    5. The formulation according to one or more of the previous claims, characterized in that it comprises:
    PVC 30-60%
    Isocyanate 20-60%
    Liquid anhydrides 3-40%
    in the presence of  
    Zeolites less than 3%
    Sodium bicarbonate less than 3%.

     
    6. A process for the production of cross-linked expanded PVC foams, characterized in that the polymeric mixture for the production of cross-linked expanded PVC foams is prepared by first introducing the liquid components, isocyanate and anhydride, into the mixer, followed by the powders of porous stabilizing and nucleating agents, and finally PVC, said process comprising a CO2 gas phase given by the following reaction between isocyanate and said liquid anhydride:

    wherein

    R1 = C6H12; C9H18; C12H24; C10H18; C13H10; C6H4; C7H5; C10H6; C16H11; C7H6

    R2 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12, said process further comprising a nucleation phase given by the presence of nucleating agents made of porous nucleating materials, and in that said CO2 gas phase and nucleating gas phase are conducted in the absence of diazocompounds, being said nucleating agents a porous zeolite, composed of aluminosilicates of the type:

            xMO • ySiO2 · zAl2O3

    wherein:

    x = 0 - 0.5

    y = 0 - 0.5

    z = 0.5 - 1

    M = Na, K, Ca, NH4, Fe,

    or a combination of said zeolite with porous sodium bicarbonate.


     
    7. The process according to claim 6, characterized in that said reaction between isocyanate and anhydride is the following:

    wherein:

    R1 = C6H4, C7H6

    R2 = C6H12; C9H18; C12H24; C10H18; C13H10; C6H4; C7H5; C10H6; C16H11; C7H6;

    R3 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12.


     
    8. The process according to any of claims 6 and 7, characterized in that it comprises:

    - preparing a polymeric mixture, obtained by first introducing the liquid components (isocyanate and anhydride) into the mixer, followed by the powders of porous stabilizing and nucleating agents, and finally PVC, the mixing of said compounds being effected under vacuum for stripping the air;

    - transferring the polymeric mixture thus obtained into a mould heated under pressure in a press, at the temperature and for the time necessary for melting the PVC and for the isocyanate-anhydride cross-linking reactions and formation of the gas phase;

    - completing the cross-linking reactions in the presence of water vapour.


     


    Ansprüche

    1. Formulierung aus Polymergemischen für die Herstellung von vernetzten PVC-Schaumstoffen des Typs, der PVC, Isocyanate, Anhydride und ein oder mehrere Keimbildner enthält, dadurch gekennzeichnet, dass die Anhydride bei Raumtemperatur flüssig sind, dass die Keimbildner aus porenhaltigen Keimbildnern bestehen und keine Diazoverbindungen vorhanden sind, wobei der Keimbildner aus porenhaltigem Zeolith besteht, der aus Aluminosilikaten folgenden Typs bestehen:

            xMO • ySiC2 · ZAl2O3

    wobei:

    x = 0-0,5

    y = 0-0,5

    z = 0,5-1

    M = Na, K, Ca, NH4, Fe

    oder eine Kombination des Zeolithen mit porenhaltigem Natriumbikarbonat.


     
    2. Formulierung nach Anspruch 1, dadurch gekennzeichnet, dass der Keimbildner porenhaltiges Natriumbicarbonat enthält.
     
    3. Formulierung nach Anspruch 2, dadurch gekennzeichnet, dass das porenhaltige Natriumbicarbonat in dem Gemisch in Mengen von weniger als 3 Gew.-% vorhanden ist.
     
    4. Formulierung nach Anspruch 3, dadurch gekennzeichnet, dass die Anhydride folgende Formel aufweisen:

    wobei
    R3 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12.
     
    5. Formulierung nach einem oder mehreren der vorangehenden Ansprüche, dadurch gekennzeichnet, dass sie Folgendes enthält:
    PVC 30-60 %
    Isocyanat 20-60 %
    Flüssige Anhydride 3-40 %
    in Gegenwart von  
    Zeolithen weniger als 3 %
    Natriumbikarbonat weniger als 3 %.

     
    6. Verfahren zur Herstellung von vernetzten PVC-Schaumstoffen, dadurch gekennzeichnet, dass das Polymergemisch für die Herstellung von vernetzten PVC-Schaumstoffen hergestellt wird, indem zuerst die flüssigen Komponenten, Isocyanat und Anhydrid, in den Mischer verbracht werden, gefolgt von den Pulvern porenhaltiger Stabilisierungsmittel und Keimbildner, und schließlich PVC, wobei das Verfahren eine CO2-Gasphase umfasst, die durch die folgende Reaktion zwischen Isocyanat und dem flüssigen Anhydrid gegeben ist:

    wobei

    R1 = C6H12; C9H18; C12H24; C10H18; C13H10; C6H4; C7H5; C10H6; C16H11; C7H6,

    R2 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12,

    wobei das Verfahren des Weiteren eine Keimbildungsphase umfasst, die durch die Gegenwart von Keimbildnern gegeben ist, die aus porenhaltigen Keimbildungsmaterialien bestehen, und dadurch, dass die CO2-Gasphase und die Keimbildungsgasphase in Abwesenheit von Diazoverbindungen durchgeführt werden, wobei die Keimbildner ein porenhaltiger Zeolith sind, der aus Aluminosilikaten folgenden Typs besteht:

            xMO - ySiC2 · ZAI2O3

    wobei:

    x = 0-0,5

    y = 0-0,5

    z = 0,5-1

    M = Na, K, Ca, NH4, Fe

    oder eine Kombination des Zeolithen mit porenhaltigem Natriumbikarbonat.


     
    7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass die Reaktion zwischen Isocyanat und Anhydrid folgende ist:

    wobei:

    R1 = C6H4, C7H6

    R2 = C6H12; C9H18; C12H24; C10H18; C13H10; C6H4; C7H5; C10H6; C16H11; C7H6;

    R3 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8; C7H10; C7H8; C4H4O2; C6H12; C7H12.


     
    8. Verfahren nach einem der Ansprüche 6 und 7, dadurch gekennzeichnet, dass er Folgendes umfasst:

    - Herstellen eines Polymergemisches, das erhalten wird, indem zuerst die flüssigen Komponenten (Isocyanat und Anhydrid) in den Mischer verbracht werden, gefolgt von den Pulvern porenhaltiger Stabilisierungsmittel und Keimbildner, und schließlich PVC, wobei das Mischen der Verbindungen unter Vakuum erfolgt, um die Luft abzuziehen;

    - Verbringen des so erhaltenen Polymergemisches in ein Formwerkzeug, das unter Druck in einer Presse erhitzt wird, bei der Temperatur und für die Zeitdauer, die für das Schmelzen des PVC und für die Isocyanat-Anhydrid-Vernetzungsreaktionen und die Bildung der Gasphase erforderlich sind;

    - Vollenden der Vernetzungsreaktionen in Gegenwart von Wasserdampf.


     


    Revendications

    1. Formulation de mélanges polymères pour la production de mousses de PVC expansées réticulées, du type comprenant du PVC, des isocyanates, des anhydrides et un ou plusieurs agents de nucléation, caractérisée en ce que lesdits anhydrides sont liquides à la température ambiante, en ce que lesdits agents de nucléation sont constitués de matériaux de nucléation poreux et en l'absence de composés diazo, ledit agent de nucléation étant constitué de zéolite poreuse, composée d'aluminosilicates du type :

            xMO • ySiO2 · zAl2O3

    dans laquelle :

    x = 0-0,5

    y = 0-0,5

    z = 0,5-1

    M = Na, K, Ca, NH4, Fe,

    ou une combinaison de ladite zéolite avec du bicarbonate de sodium poreux.


     
    2. Formulation selon la revendication 1, caractérisée en ce que ledit agent de nucléation comprend du bicarbonate de sodium poreux.
     
    3. Formulation selon la revendication 2, caractérisée en ce que ledit bicarbonate de sodium poreux est présent dans le mélange en des quantités inférieures à 3 % en poids.
     
    4. Formulation selon la revendication 3, caractérisée en ce que lesdits anhydrides ont la formule :

    dans laquelle
    R3 = C6H6; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8 ; C7H10 ; C7H8 ; C4H4O2 ; C6H12 ; C7H12.
     
    5. Formulation selon une ou plusieurs des revendications précédentes, caractérisée en ce qu'elle comprend :
    PVC 30-60 %
    Isocyanate 20-60 %
    Anhydrides liquides 3-40 %
    en présence de  
    zéolites moins de 3 %
    bicarbonate de sodium moins de 3 %

     
    6. Processus pour la production de mousses de PVC expansées réticulées, caractérisé en ce que le mélange polymère pour la production de mousses de PVC expansées réticulées est préparé en introduisant d'abord les composants liquides, l'isocyanate et l'anhydride, dans le mélangeur, suivis des poudres d'agents de stabilisation et de nucléation poreux, et enfin du PVC, ledit processus comprenant une phase de gaz CO2 donnée par la réaction suivante entre l'isocyanate et ledit anhydride liquide :

    dans laquelle

    R1 = C6H12; C9H18; C12H24; C10H18; C13H10; C6H4; C7H5; C10H6; C16H11 ; C7H6

    R2 = C6H6; C7H6; C6H8; C6H10 C14H26; C3H4; C3H6; C5H10; C10H18 C4H8; C7H10; C7H8; C4H4O2; C6H12 ; C7H12,

    ledit processus comprenant en outre une phase de nucléation donnée par la présence d'agents de nucléation composés de matériaux de nucléation poreux, et en ce que lesdites phase de gaz CO2 et phase de gaz de nucléation sont menées en l'absence de composés diazo, lesdits agents de nucléation étant une zéolite poreuse, composée d'aluminosilicates du type :

            xMO • ySiO2 · zAl2O3

    dans laquelle :

    x = 0-0,5

    y = 0-0,5

    z = 0,5-1

    M = Na, K, Ca, NH4, Fe,

    ou une combinaison de ladite zéolite avec du bicarbonate de sodium poreux.


     
    7. Processus selon la revendication 6, caractérisé en ce que ladite réaction entre l'isocyanate et l'anhydride est la suivante :

    dans laquelle

    R1 = C6H4, C7H6

    R2 = C6H12; C9H18; C12H24; C10H18; C13H10; C6H4; C7H5; C10H6; C16H11 ; C7H6 ;

    R3 = C6H6 ; C7H6; C6H8; C6H10; C14H26; C3H4; C3H6; C5H10; C10H18; C4H8 ; C7H10; C7H8 ; C4H4O2; C6H12 ; C7H12.


     
    8. Processus selon l'une quelconque des revendications 6 et 7, caractérisé en ce qu'il comprend :

    - la préparation d'un mélange polymère, obtenu en introduisant d'abord les composants liquides (isocyanate et anhydride) dans le mélangeur, suivis des poudres d'agents de stabilisation et de nucléation poreux, et enfin du PVC, le mélange desdits composés étant effectué sous vide pour retirer l'air ;

    - le transfert du mélange polymère ainsi obtenu dans un moule chauffé sous pression dans une presse, à la température et pendant le temps nécessaires pour faire fondre le PVC et pour les réactions de réticulation d'isocyanate-anhydride et la formation de la phase gazeuse ;

    - la réalisation des réactions de réticulation en présence de vapeur d'eau.


     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description