BE1024176B1 - Filling moisture-sensitive products in a tube - Google Patents

Abstract

A process has been described for producing a composition which can cure under the influence of moisture, in which the reactive end groups of a reactive polymer are reacted with a cross-linker or cross-linker to form the prepolymer, the product being filled in a plastic sleeve as final package and the sleeve after filling is sealed by placing a "kolb" or plunger in the open end of the sleeve, characterized in that the sleeve on the inside, at least at the place where the kolb must come into contact with the tube, is provided with a thin layer of lubricant.

Description

Filling moisture-sensitive products in a tube

SCOPE OF THE INVENTION

The present invention relates to the production of moisture sensitive products. More in particular, the invention relates to the manufacture of products that are applied locally with some precision, for example by pressing them from a tube or sausage-like package through a nozzle, and thus can be used as a sealant, as an adhesive, as a stuffing material or as an insulating material, with the common characteristic that all these substances, after application, somehow react further with water or moisture, usually from the air or from the immediate environment from where the substances were applied, to their final crosslinking To form a 3-dimensional structure, also called curing, and thus to obtain the final properties for which they are used.

BACKGROUND OF THE INVENTION

An important example of products that eventually cure due to reaction with water or moisture can be found in the family of kitten and mastics ("caulks, mastics and sealants").

Kitten or mastics - the two terms used in this document as synonyms of each other - are offered with a wide range of properties ranging from "elastic" to "pseudo-plastic" to "plastic" depending on their response to distortion in their final state, also referred to as "elastic shape recovery" or the "sustainably permissible deformation" complementary thereto, by which is meant the possibility of a kit returning, after stretching, to its original shape or the deformation that remains thereafter in the longer term The possibility of "permanently permissible deformation", which in practice is the maximum movement that a joint may have in practice, varies from typically not more than 7-8% for plastic products, which often have no shape recovery at all after repeated deformation. , about 1015% sustainably permissible deformation for plasto-elastic products, up to at least 20% for the truly pure elastic product and. In the case of plastic and pseudo-plastic sealants, curing occurs very often mainly through physical drying, i.e. through the evaporation of some solvent, including water, from the composition

The family of elastic sealants and mastics, on the other hand, is mainly populated by products that cure by chemical reaction with water or moisture. The terms water and moisture are used interchangeably and synonymously in this document, since the invention relates to the reaction with water (H2O), and the invention makes no distinction between the state of aggregation or the purity of the water that would be available for that reaction.

These elastic sealants are usually manufactured on the basis of silicone or polyurethane (PUR), but also hybrid sealants, based on "silane modified polymers" (SMP) with, for example, a polyurethane or a polyether backbone or main chain (also called " backbone) are well known. Their ability to "elastic shape recovery" can go up to over 70% and often even to more than 90%, a characteristic why they are highly sought after, both by professionals and do-it-yourselfers, in the construction and construction industry, such as for the installation of glazing, in sanitary applications, for elastic bonding in the glass and metal sector, for seals on cars, boats, caravans, for installing connection joints and expansion joints, and so on.

The silicone sealants represent by far the largest part of this elastic sealant in the market. The production of elastic silicone sealants is based on a reactive polysiloxane polymer, with on each silicon atom usually in each case two organic groups protruding sideways from the backbone of the silicon oxide polymer, usually a polydimethylsiloxane. The polymer is reactive because there is a still reactive group at both ends of the otherwise generally straight [-R 2 Si-O] n chain, usually a hydroxyl function. In the most traditional silicone sealant production, the first chemical step is to react the reactive end group of the polysiloxane polymer with a certain cross-linker or cross-linker to form the so-called "prepolymer", which is then still capable of to harden by crosslinking. This reaction step is sometimes also referred to as "end-capping," i.e., adding another end group to the reactive polymer. Because this step leads to the formation of a "prepolymer", this reaction step is often also called "prepolymerization". This step prepares the reactive polymer for the later polymerization reaction, without itself doing any polymerization. The term prepolymerization is therefore not incorrectly chosen, but must therefore be interpreted and read in that sense.

Most conventionally, an alkyl triacetoxy silane is used as crosslinker, for example ethyl triacetoxy silane, one of the three acetate functions reacting with the hydroxyl group of the polymer, whereby an additional Si-O-Si (siloxane) compound is formed when a molecule of acetic acid is released. In this way, the polysiloxane polymer receives two acetoxy functions on both sides of the siloxane chain, i.e. two reactive end groups on each side. These remaining reactive groups are intended to react after application of the silicone paste with moisture from the environment to form a new siloxane compound between two polymer chains, again on release of a molecule of acetic acid. Because each end of the original dialkyl siloxane polymer has received two reactive end groups from the cross-linker, a three-dimensional, cross-linked end structure is created in this way under the influence of ambient water or moisture. In addition to this technique based on alkyl triacetoxy silane, alkoxy and oxime technologies are also known. In addition, benzamide, lactate, and / or enoxy technologies can also be found, although to a significantly lesser extent.

During the production of the silicone kit, additional additives or additives are usually incorporated for a number of reasons, such as plasticizers, extenders, fillers, pigments and / or dyes, and adhesion promoters. To accelerate cross-linking in the final application. a catalyst is usually also added. In order to ultimately form a paste during production that is suitable for easy application of the end product, at least one thickener is added to change the rheology, most typically silica (SiO 2), whereby the still relatively liquid reaction product rises to a paste that is primarily a visco-elastic material. The final paste must then still be filled in a suitable container, often a plastic tube from which the silicone kit can be injected under some pressure through a nozzle to its final destination.

To allow good crosslinking after application of the kit, it is important that the two reactive end groups on the siloxane polymer are still available after application of the silicone kit from its container to its final destination. They may not yet have had the opportunity to react, such as during the production, transport or storage of the silicone kit, i.e. before it is used in its end application.

It is therefore very important that moisture or water, in whatever form, is prevented from reacting prematurely with the reactive groups of the moisture sensitive products, in the case of silicone sealants, the reactive end groups on the siloxane polymer, such as those caused by it the reaction with the crosslinker must be applied. Such premature reaction of the reactive groups with moisture or water leads to premature cross-linking of the polymer chains in the blend, which can lead to a variety of problems. For example, during production this can lead to the creation of "sheets" ("flakes") in the end product, ie lumps of cross-linked polymer that are no longer reactive, that interfere with application and that can properly affect the final appearance of the applied paste. to disturb. But premature crosslinking during production can also lead to increased adhesion of the product to the production equipment, which can considerably increase the cleaning costs and maintenance frequency and reduce the production capacity of an installation. Even after production, i.e. during storage and / or transport of the packaged mastic to the end user, premature crosslinking can occur due to the introduction of more moisture or water, so that the product becomes unusable. Even after the purchase, i.e. from the end user, this phenomenon can still occur, in the sense that the purchased package would not reach its desired and / or prescribed shelf life.

The present invention is concerned with reducing the risk of premature cross-linking of the moisture-sensitive products during their production, transport or storage up to the final application, in particular with the intention of extending the shelf life of the packaged end product and / or improve the stability of the packaged end product.

The present invention has for its object to provide for the avoidance or at least alleviation of the problems described above and / or general improvements.

SUMMARY OF THE INVENTION

According to the invention there is provided a method as defined in any of the appended claims.

In one embodiment, the present invention provides a method for manufacturing a product that can cure under the influence of moisture, wherein the product is filled in a plastic tube as a final package and the tube is sealed after being filled by the open end of the to place a "kolb" or plunger in the sleeve, characterized in that the sleeve is provided with a thin layer of lubricant on the inside, at least at the place where the kolb must come into contact with the sleeve.

The layer of lubricant first of all ensures a good seal between the plunger and the tube, so that air or moisture cannot easily find their way to the product in the tube and thereby the shelf life of the filled tube is extended. The layer of lubricant has the additional advantage that the plunger can be pressed more easily and with less force to force the product out of the tube. Moreover, the layer of lubricant reduces the risk that the plunger would twist during use of the filled tube and that air and / or moisture could thereby penetrate into the tube and lead to premature crosslinking of the product in the tube.

The terms "kolb" and "plunger" are used interchangeably and synonymously in this document.

This layer of lubricant preferably has a thickness of no more than 0.20 mm, more preferably at most 0.15 mm, even more preferably at most 0.10 mm, still more preferably at most 0.05 mm. Optionally, this layer preferably has a thickness of at least 0.01 mm, preferably at least 0.02 mm, even more preferably at least 0.03 mm, still more preferably at least 0.05 mm, preferably at least 0.07 mm, and more preferably at least 0.10 mm.

Many substances or compositions are suitable as lubricants for the inner wall of the tube.

A requirement is that the lubricant contains little to no water, preferably at most 100 ppm by weight of water, more preferably at most 10 ppm by weight. This offers the advantage that the lubricant cannot additionally bring a significant amount of water into contact with the packaged product, and thereby cause premature cross-linking.

The lubricant also preferably has a low volatility, for example expressed as a low vapor pressure at room temperature (23 ° C), preferably a vapor pressure at room temperature of at most 1.0 hPa, more preferably at most 0.50 hPa, and even more preferably at most 0.10 hPa. This offers the advantage that as much of the applied amount of lubricant as possible remains where it was applied and thus remains available to fulfill its useful function, instead of volatilizing and no longer being available to lubricate the plunger in the tube .

Suitable lubricants are, for example, silicone oils, but possibly also high-boiling hydrocarbons, preferably high-boiling saturated hydrocarbons, such as paraffins or isoparaffins, although the lubricating capacity of these hydrocarbons only becomes sufficiently important at a sufficiently high molecular weight or carbon number, so that a desired fluidity at a certain temperature can often be better achieved with branched hydrocarbon chains than with their straight-chain variants.

Often also suitable as a lubricant for the kolb or plunger, one of the plasticizers selected in the formulation of the composition is filled into the tube. The latter are preferred by the applicants because of their compatibility with the composition itself. Mainly for compatibility reasons, the inventors in silicone sealants preferably use silicone oil to lubricate the head. In hybrid and / or PUR-based mastics, the plasticizer often used is the plasticizer used in the formulation of that kit. The lubricant can be liquid or solid at room temperature. The inventors preferably use a lubricant that is liquid at ambient temperature (10 ° C) so that it can be applied at a low temperature with little or no use of heating.

In one embodiment, the lubricant is a silicone oil, preferably a non-reactive polysiloxane, more preferably a non-reactive polydimethylsiloxane. The silicone oil has the advantage that the lubricant is chemically inert and very stable, and also very compatible with the moisture-sensitive product in the tube, especially if this is a silicone-based kit, or more technically correct based on siloxanes. In one embodiment, the silicone oil is sprayed or sprayed into the still empty tube. In another embodiment, the lubricant is dripped onto the plunger on its way to where it is introduced into the sleeve.

In one embodiment, the sleeve is pre-lubricated with a thin layer of wax as a lubricant, preferably a hydrocarbon wax, more preferably a saturated hydrocarbon wax. The wax may be, for example, a polyethylene wax or a mineral wax recovered from the heavy fractions from petroleum distillation. The wax can also be a triglyceride. The lubricant is preferably applied in the form of an aqueous or solvent-containing dispersion or emulsion. This is then preferably sprayed in the back of the tube. After application, the water or solvent then evaporates and the wax remains to serve as a lubricant when the head or plunger is inserted into the tube.

DETAILED DESCRIPTION

The present invention will be described below in certain embodiments and with any reference to certain drawings, but the invention is not limited thereto, but only by the claims. The possible drawings are only schematic and not restrictive. In the drawings, some of the elements may be exaggerated and not drawn to scale for illustrative purposes. The dimensions, also relative, in the drawings therefore do not necessarily correspond to how the invention is practiced.

In addition, the terms, first, second, third, and the like, are used in the description and in the claims to distinguish between similar elements and not necessarily to describe a sequential or chronological order. These terms are interchangeable under appropriate conditions and the embodiments of the invention may occur in sequences other than those described and illustrated herein.

In addition, the terms top, bottom, over, under, and the like in the description and in the claims are used for descriptive purposes and not necessarily to indicate relative positions. These terms thus used are interchangeable under appropriate conditions and the embodiments of the invention may occur in sequences other than those described and illustrated herein.

The term "include", as used in the claims, should not be construed as limiting to the elements listed in context therewith. It does not exclude the presence of other elements or steps. It is to be considered as prescribing the presence of said characteristics, numbers, steps or components as prescribed, but does not exclude the presence or addition of one or more other characteristics, numbers, steps or components, or groups thereof. Thus, the scope of "an article comprising means A and B "Are not limited to an object consisting solely of means A and B. It means that A and B are the only elements of interest to the object in connection with the present invention. Accordingly, the terms "include" or "include" also include the more limited terms "essentially consist of" and "consist of". Thus, by replacing "include" or "embed" with "consist of", these terms represent the basis of preferred but narrowed embodiments, which are equally provided as part of the contents of this document with respect to the present invention.

The products manufactured with the method according to the present invention are generally characterized in that they form a pasty substance that remain in place after application, usually locally and with some precision by pressing them through a nozzle. For example, those products that are mastic or sealants can usually be coated and / or flat coated within a time after application as still uncured paste, and thereby achieve a good seal after curing. The product paste for curing is therefore usually characterized by a very high so-called "complex viscosity" when low shear forces act on the product, so under low shear forces. The "complex viscosity" is determined by oscillation, so that the viscous and elastic contribution can be separated to the rheological response. Under low shear forces, the paste preferably behaves as well as a solid. Nevertheless, it is desirable that the pressing of the paste through the nozzle does not require excessive forces. Therefore, it is desirable for the paste to have a lower complex viscosity prior to curing at higher shear forces. The product paste thus preferably has a high shear thinning effect. At high shear forces, the paste therefore preferably behaves more like a liquid.

But the properties after curing are also important and can vary considerably. Some mastics or kittens are expected to remain plastic after hardening but therefore have little recovery capacity after deformation. The durable permissible deformation of a "plastic" kit is generally not higher than 7.5%, which means that the product can only handle a deformation of at most 7.5% in order to be able to return to its original state after the deforming force has been lost. such a deformation there is permanent deformation.Other sealants are expected to have a plasto-elastic behavior.These sealants have a permanent permissible deformation that is higher than that of plastic sealants, usually of around 12.5%, but the majority of the mastic or kitten is rather "elastic", and can (almost) fully recover with deformations of 20% or more. For example, most silicone sealants have an elastic shape recovery of more than 90%. But there is also a demand for products with very different properties within the elastic sealant.

Each product in the family of products made by the method of the present invention is therefore an accurate balance between properties of the uncured paste and those of the final cured product after application. Time and again the combination of properties is the result of a careful choice of ingredients and the quantities that are incorporated. Each component has an interest in this, such as the choice of the reactive polymer and the nature of the cross-linker, but also whether or not the other possible ingredients are used, such as plasticizers, extenders, fillers, thickeners, additional adhesion promoters, and catalysts.

Within the context of the present invention, reactive polymers is understood to be a reactive polymer of silicon oxide, with a backbone formed by alternating silicon and oxygen atoms. Sideways on that linear backbone of the silicon oxide polymer there are organic side groups on each silicon atom, usually saturated organic groups, and preferably methyl groups so that the reactive polymer is a polydimethylsiloxane. This reactive polymer is a result of a polymerization reaction. Each polymer molecule is therefore characterized by a certain chain length, and a mixture of molecules is usually characterized by a distribution of that chain length among the various molecules. Usually the average chain length of the molecules in a mixture is already sufficiently characteristic to be able to distinguish different reactive polymer raw materials from each other. An average molecular weight (g / mol) can also be mentioned as a characteristic for a polymer composition, although a strong spread of the molecular weight over the different polymer molecules in the composition must be kept in mind.

As the average chain length of a reactive polymer or polymer mixture increases with the same choice of organic side groups, the dynamic viscosity of the polymer or mixture will also increase. This viscosity is expressed in Pascal seconds (Pa.s). It is therefore common to partially characterize the reactive polymer products by their viscosity. For example, very common reactive polydimethylsiloxanes have a viscosity at 20 ° C in the range of 20350 Pa.s, for example those indicated by type 20 (20 Pa.s), 50 (50 Pa.s), 80 (80 Pa. s), 120 (120 Pa.s), 150 (150 Pa.s) and 350 (350 Pa.s). Suitable reactive polymers are available under the name Polymer FD from Wacker, Xiameter OHX from Dow Corning or Xiameter, Silopren E from Momentive Performance Materials, or Bluesil FLD from Bluestar.

The inventors have found that the reactive polymers with a higher viscosity, and therefore with a higher chain length, form reliable end products in comparison with the reactive polymers with a lower viscosity.

The polymer molecule remains reactive because of the end group, usually at both ends of the backbone, which is usually a hydroxyl group or function. It is with this end group that the crosslinker or cross-linker responds. The crosslinker is there to retain more than one reactive and available end group after the reaction with the end group on the reactive polymer.

In the context of the present invention, the reaction product of the reactive polymer with the crosslinker is called an encapsulated prepolymer. The reaction of the crosslinker with the reactive polymer, with which a molecule of crosslinker in each case adheres to one of the reactive end groups of the reactive polymer, is then called the prepolymerization. After all, curing under the influence of water or moisture is the polymerization.

It is the supply of at least two reactive end groups at each end of the encapsulated prepolymer, wherein the reactive end groups can react with each other under the influence of water or (air) humidity, which allows the final formation of a 3-dimensional structure, which is allowed mentions curing (polymerization).

Plasticizers are added to influence the rheological behavior of the uncured paste, but also to help determine the elasticity and resilience of the cured end product. A good choice and dosage of the plasticizer can thereby reduce the amount of thickener required to achieve a desired paste thickness. Suitable plasticizers are, for example, the so-called silicone oils, which are non-reactive siloxanes such as polydimethylsiloxane, and which are offered in different qualities with, for example, different chain lengths. The siloxanes are extremely suitable because they have a high compatibility with the other ingredients of the end product, in particular with the prepolymer. Very common non-reactive polydimethylsiloxanes have a viscosity at 20 ° C in the range of 100 mPa.s to 12500 mPa.s. Such products are offered, among others, under the name Plasticizer W by the company Momentive Performance Materials, or as Weichmacher by the company Wacker.

Often at least a portion of the plasticizer can be replaced with a high boiling solvent. For example, hydrocarbons or mixtures thereof with a high boiling range and therefore very low volatility are suitable. Such products are offered, for example, as Exxsol D60, D80, D100, D120 or D140, or as Isopar H, J, K, L, M, N or V from ExxonMobil Chemical, or Ketrul D100, Hydroseal G232H, G240H, G3H , G250H, G270H, G400H, G310H, G315H, G340H from Total, or Shellsol D60, D80, D100 from Shell, Pilot 261, 291, 321, 400, 600, 900 from Petrochem Carless, or Nyflex 8120 , 8131, 800 from Nynas.

The choice of the crosslinker has an important influence on the properties of the end product.

The inventors prefer as cross-linker a compound consisting of a silicon atom with 3 reactive groups and 1 non-reactive group thereon. The three reactive groups are intended to react upon curing, and provide the ability to build the intended three-dimensional network. The choice of the last non-reactive group makes it possible to help determine the properties of the end product.

In silicone sealants, the inventors use, among other things, alkyl triacetoxy silane as a crosslinker. These so-called "acetic acid" cross-linkers lead to rather "tough-elastic" products, which are also characterized by some acidity. They can be used without any problem in the majority of end applications, mainly for the execution of glazing, sanitary applications, elastic bonding in the glass and metal sector, or for seals on cars, boats or caravans. They are less suitable for alkaline substrates such as concrete or cemented substrates, or for certain metals, such as copper. The inventors prefer to use ethyl triacetoxy silane. However, the methyl, propyl and vinyl equivalent variants are also known and suitable. The ethyl form has the advantage that it is liquid under standard conditions, so that it can be easily processed and incorporated into the composition. Mixtures of the methyl and ethyl form are also widely used because most forms are liquid. Commonly used as "acetic acid" crosslinkers are methyltriacetoxysilane, ethyltriacetoxysilane, propyltriacetoxysilane, and mixtures thereof. Suitable products are, for example, Crosslinker ES21, ES23, ES24 available from Wacker, Crosslinker 3034, 3187 from Momentive Performance Materials, Crosslinker MTA, ETA , PTA, ETA / MTA (70/30), PTA / MTA (70/30) from Nitrochemie, Crosslinker AC 10, 15, 30 from Evonik Hanse.

For the bonding of polyvinyl chloride (PVC) plastic materials, alkaline substrates, and for porous substrates, the inventors prefer silicone sealants with a rather neutral composition in terms of acids and acid development, and thus based on cross-linkers other than triacetoxy silanes. Neutral silicone sealants preferably manufacture the inventors with one or more alkoxy-based silanes, such as alkyl trialkoxy silane, preferably methyl trimethoxy silane or vinyl trimethoxy silane, or with one or more oximes as a substituent on the silicon of the cross-linker, although benzamide whether lactate is also suitable. Among the oxime-based cross-linkers, methyl ethyl ketoxime (more fully methyl ethyl ketone oxime, often abbreviated as "MEKO", CH3-CH2- (CH3) C = N-OH) is a well-known substituent. Other known substituents for the silicon of a silane crosslinker are acetone oxime, MIBKO or methyl isobutyl ketone oxime, and MPKO or methyl propyl ketone oxime.

Suitable oxime-based cross-linkers are methyl tris (MEKO) silane, vinyl tris (MEKO) silane, tetrakis (MEKO) silane, methyl tris (MIBKO) silane, vinyl tris (MIBKO) silane, methyltriacetonoxime silane, ethyltriacetonoxime silane, vinyltriacetonoxime silane, methyl tris (MPKO) silane, vinyl tris (MPKO) silane, and mixtures thereof. Suitable products are, for example, Crosslinker MOS, VOS, TOS, MT10, MT15, VT5, VT2, VT1, LM43, LM100, LM200, LM400, OS1600, OS2600 from the company Nitrochemie, Crosslinker OX10, OX20, OX30, OX32, OX33 from the Evonik Hanse.

Suitable alkyl, alkenyl or phenyl trialkoxy crosslinkers are, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilaan, methyltriethoxysilane, propyltriethoxysilane, isobutyl-triethoxy silane, vinyltriethoxysilane, phenyltriethoxysilaan, octyltrimethoxy-silane, octyltriethoxysilane, and mixtures thereof. Suitable products are, for example, Silquest A-1630, Silquest A-171 available from Momentive Performance Materials, Geniosil® XL-10, Crosslinker ME60, ME63, Geniosil GF56 from Wacker, Crosslinker MTMS, Dynasylan® VTMO (Evonik); Vinyl trimethoxysilane, Vinyl triethoxysilane from the company Nitrochemie.

An adhesion promoter can also be incorporated into the mastic. Suitable adhesion promoters are, for example, organosilanes, preferably amino silanes or epoxy silanes. Suitable adhesion promoters are found, for example, in the product families that are offered as Geniosil from Wacker, as Silquest from Momentive Performance Materials, and as Dynasilan from Evonik.

Very suitable as adhesion promoters are, for example, di-tert-butoxy-diacetoxysilane for the "acetic acid" products, but also suitable for neutral products are 3-aminopropyl-triethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane 3- (2-aminoethylamino) propyltriacetoxysilane, N- (3-trimethoxysilylpropyl) diethylenetriamine, bis- (3-methoxysilylpropyl) amine, aminoethylaminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyldilethoxymethyl-dimethoxymethyl-nil-3-methyl-3-propyl -aminopropyltrimethoxy-silane, N- (n-butyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyl-diethoxysilane, aminoethylamino-propyltrimethoxysilane 3-glycidoxypropyl-trimetoxysilane-3-propyl-triisopropyl-propane-3-ethoxysilane-3-propylopropylene oxide terminated, polydimethylsiloxanes with aminoalkyl groups, polydimethylsiloxanes reaction product with N- (3-trimethoxysilyl) propyl) cyclohexanamine, alkoxypolysiloxanes aminoalkyl modified groups, multifunctional amino silanes, and functional oligosiloxanes.

Various substances can serve as a thickener. The inventors prefer silica as a thickener, because of the reinforcing effect that silica can have on the product properties. Silica is a weak acid derived from silica, SiO 2, with the general formula Si 2 n 2 H 2 O, where n may differ.

Silicic acid is preferred because it enters into chemical bonds with the backbone or backbone of the polymer, resulting in a significant enhancement of the physical and mechanical properties of the end product. The inventors have found that various forms of silica can serve as a thickening agent, but the inventors prefer to use fumed silica or "pyric silica" because the intended effects are even more pronounced. It is primarily the tear strength of the end product that increases. This interaction between the thickener and the polymer is much smaller or non-existent in many possible alternatives, and is therefore the main reason for the inventors to choose silica.

A thickener is needed in many formulations to eventually form a paste, capable of being pressed through a nozzle to be applied at the desired location. In silicone sealants, the inventors preferably use silica or silica as a thickener. Suitable thickeners are available, for example, as HDK® V15, V15A, N20, H13L, H15, H18 from Wacker, as Cabosil® L-90, LM-150, M-5, TS-610, TS-622 from the company Cabott, as Aerosil® 130, 150, 200, R972, R974 from Evonik.

Unless a transparent end product is desired, the formulation of the moisture-curing end product may also contain one or more fillers. Suitable fillers are, for example, chalk or dolomite, in finely divided form. Those fillers can be obtained by grinding or by precipitation. The filler can also be coated with a suitable coating. Fillers with a coating or coating generally contain less moisture at the end of their production, and also appear to have less tendency to absorb moisture after their production, such as during storage, transfer or transport. Coated fillers can have a reinforcing effect on the end product, and thus positively influence the mechanical properties of the end product. Suitable fillers are found, for example, in the product families natural calcium carbonates, precipitated calcium carbonates, calcium-magnesium carbonates (also known as "dolomite"), which are offered by a long range of suppliers, such as Omya, Imerys and Alpha Calcite.

A catalyst is often added to make the final cure faster. The catalyst makes the product much more sensitive to moisture. Therefore, a catalyst is preferably added very late in the production process, if possible even as the last ingredient of the formulation, possibly followed by pigment and / or fungicide. The traditional catalysts were mostly based on tin (Sn). More modern catalysts are based on titanium (Ti), preferably in the form of titanates, or on bismuth (Bi), and are preferable primarily for ecological reasons. Suitable catalysts can be found, for example, in the following product ranges: dibutyltin diacetate, dioctyltin diacetate, dibutyltin-dilaurate, dioctyltin dilaurate, dibutyltindicarboxylaat, dioctiltindicarboxylaat, dibutyltindineodecanoaat, dioctyltindineodecanoaat, dibutyl tin oxide mixtures, dioctyltin oxide mixtures, tetraisopropyl orthotitanate, titaniumacetylacetonaat and other titanium and / or bismuth-based catalysts . Suitable catalysts are also available which are based on Calcium (Ca) and / or Zinc (Zn).

Suitable products are, for example, the catalysts sold under the TIB KAT® brand name, such as types 216, 217, 218, 219, 221, 223, 226, 229, 232, 233, 248 and 318, available from TIB Chemicals AG.

In one embodiment, the present invention provides a method of manufacturing a moisture-curable composition in which the reactive end groups of a reactive polymer are reacted with a cross-linker or cross-linker to form the prepolymer, characterized by in the reaction to form the prepolymer, the crosslinker is added in a stoichiometric excess with respect to the amount of reactive end groups present on the reactive polymer.

The crosslinker is a compound with at least three reactive groups, one reactive group of which during the so-called "prepolymerization" step ensures the reaction with a reactive end group of the reactive polymer to form the so-called prepolymer. As a result, at least two reactive groups remain to be able to form a three-dimensional structure later in the application of the paste and under the influence of moisture as part of the curing reaction. The crosslinker itself thus necessarily has at least two, usually three, and sometimes even four reactive groups per molecule that can react with moisture.

We have found that the amount of the crosslinker that is added in excess fulfills a useful function as a potential moisture scavenger for when some moisture would find its way into the prepolymer composition prematurely. crosslinker is available to react with the prematurely penetrating moisture, leaving less moisture to react with the prepolymer and thus prematurely leading to some curing of the composition.The inventors have found that using a stoichiometric excess of crosslinker in the prepolymerization step significantly extends the shelf life of the end product The excess crosslinker acts as a moisture trap during the production of the kit, during filling and packaging, as well as during storage, transport and trading of the packaged kit to the end user , and also afterwards, if the end user does not use the kit immediately, or only partially used and want to use the remaining amount some time later.

The reactive polymer is usually straight-chain in structure and each molecule has two reactive end groups. During prepolymerization, these two end groups each react with one molecule of crosslinker. The stoichiometric ratio of "crosslinker / reactive polymer" is therefore 2.0: 1. Thus, in the method according to the present invention, an excess of crosslinker is added, i.e. the molar ratio of "crosslinker / reactive polymer" is greater than 2.0: 1 .

Preferably, applicants use a molar ratio of crosslinker to the number of molecules of reactive polymer present of at least 3.0: 1.0, preferably at least 5.0: 1.0 molar, more preferably at least 10: 1 molar, even more preferably at least 12: 1 molar, preferably at least 15: 1, more preferably at least 18: 1, even more preferably at least 20: 1 and still more preferably at least 22: 1 molar.

The inventors have also found that an excessive excess of cross-linker can negatively influence the properties of the end product. Therefore, the inventors prefer a molar ratio of crosslinker to the number of molecules of reactive polymer present of at most 60: 1 molar, preferably at most 55: 1 molar, more preferably at most 50: 1 molar, even more preferably at most 45: 1 molar, preferably at most 40: 1 molar, more preferably at most 35: 1, even more preferably at most 30: 1, and still more preferably at most 25: 1 molar.

The most appropriate amount of excess, however, depends on the final kit composition and the care with which the composition is handled during mixing and filling, including the further measures taken to avoid moisture problems.

For example, the inventors prefer to use more excess in a kit composition with filler than in a kit composition without filler. In a so-called "filled" kit composition, the inventors therefore preferably use a molar ratio of "cross-linker / reactive polymer" that is at least 20% higher than in a corresponding "unfilled" kit composition, more preferably at least 25% higher, with even more preferably at least 30% higher and still more preferably at least 33% higher As the upper limit, the inventors prefer to use at most 50% higher molar ratios for filled kit compositions than in a corresponding "unfilled" kit composition, preferably at most 45% higher, more preferably at most 40% higher.

The amount of excess crosslinker, or the molar ratio of "crosslinker / reactive polymer", which is most appropriate for use in a certain kit composition, within a certain process and with a certain mixing and filling installation, is therefore best case by case and determined empirically.

To determine the "crosslinker / reactive polymer" molar ratio, the applicants take the molecular weight of the crosslinker on the one hand, if this is a mixture, take the average molecular weight of the crosslinker mixture based on the number made. In the case of a polymer, the applicants calculate the average molecular weight that can be calculated based on the number of recurring monomer units In the case of an OH-terminated polydimethylsiloxane, the recurring unit is [-O-Si (CH3) 2-] with a weight of 74, so that a reactive polymer with 1000 recurring units has 1000 x 74 + 18 = 74018 as the average molecular weight The weight units used are converted with these molecular weights into the number of molar units used, which can then be used to calculate the "crosslinker / reactive polymer" molar ratio.

In one embodiment, the present invention provides a method for manufacturing a product that can cure under the influence of moisture and that contains one or more fillers, the filler being formed either by milling or by precipitation or precipitation, characterized in that the milled filler contains no more than 2000 ppm weight of water, and the precipitated filler contains no more than 8000 ppm weight of water.

The inventors have found that the use of fillers according to the present invention makes it possible to produce sealants with a sufficiently long shelf life after filling and packaging, and also to reduce the risk of the formation of sheets ("flakes") below an acceptable level during production to keep.

A ground filler is generally a powder with a d50 of more than 1.0 µm, preferably at least 1.5 µm, more preferably at least 2.0 µm, even more preferably at least 3.0 µm, and even more preferably at least 5.0 µm.

Preferably, the ground filler contains at most 1500 ppm by weight of water, more preferably at most 1000 ppm, even more preferably at most 800 ppm and even more preferably at most 600 ppm water.

A suitable example of a ground filler is ground calcium carbonate or ground calcium carbonate (GCC).

Preferably the precipitated or precipitated filler comprises at most 7500 ppm by weight of water or moisture, more preferably at most 7000 ppm by weight of water, even more preferably at most 6500 ppm, still more preferably at most 6000 ppm, preferably at most 5500 ppm, more preferably at most 5000 ppm weight, preferably at most 4000 ppm, more preferably at most 3000 ppm, even more preferably at most 2500 ppm, and still more preferably at most 2000 ppm weight at water or moisture.

A suitable example of a precipitated filler is precipitated calcium carbonate or precipitated calcium carbonate (PCC).

Theoretically, the most suitable filler for the process according to the present invention best has no residual moisture at all, and thus comprises less than 1 ppm of water. However, this level is not very practically and economically feasible for producers. The inventors have found that the following lower limits for the water content of the fillers are workable and thus reflect their preference.

Preferably, the ground filler comprises at least 100 ppm by weight of water, more preferably at least 300 ppm, more preferably at least 500 ppm.

With the precipitated filler, the practically and economically feasible lower limit is somewhat higher. Preferably the precipitated filler comprises at least 1000 ppm of water, more preferably at least 1500 ppm, even more preferably at least 2000 ppm.

Allowing a small amount of water, but still suitable for the process, into the filler used brings the advantage that the process for manufacturing the filler is simpler, which improves the availability of the filler from a wider range of sources and providers, so that there is a wider choice of options on economically more favorable terms.

In one embodiment, the method according to the present invention comprises pneumatically transporting the filler to the mixing plant where the filler is mixed in at least one of the liquid ingredients required to obtain the end product. In the pneumatic transport embodiment, the carrier for pneumatic transport is preferably a gas with a dew point of at most 0 ° C, preferably at most -10 ° C, more preferably at most - 20 ° C, at even more preferably at most -30 ° C, still more preferably at most -40 ° C, and preferably at most -45 ° C.

Various gases are suitable as carriers for this pneumatic transport, such as natural gas, methane, CO2 or nitrogen. Preferably, however, the inventors use nitrogen or air for the pneumatic transport. This offers the advantage that the gas is non-flammable, so that the risk of fire or explosion is kept as low as possible, both during transport and during the supply, treatment and removal of the gas.

Even more preferably, the inventors use air for the pneumatic transport, whereby preferably ambient air is pressurized and dried to the desired dew point before the air is used for the pneumatic transport. For example, the air can be dried by passing the air over a moisture adsorbent such as a molecular sieve or silica gel.

Preferably, the inventors dry the air by cooling it to a temperature of at most the desired dew point, whereby the excess of moisture in the air condenses and can be physically separated, and whereby a dried air remains with a moisture content of at most the desired dew point. The advantage of this drying method is that the installation can be operated continuously, and that no moisture adsorbent must be regenerated when such agent has become at least partially saturated with moisture.

The inventors prefer to determine the dew point of a gas by means of a polymer sensor, such as the Dewpoint transmitter testo 6740 available from Testo Inc., with its head office in Germany.

The inventors preferably determine the water content of a filler with the analysis method according to DIN 51777 based on a titration according to the Karl-Fischer analysis method and adapted for samples of powders or other solids, and is expressed relative to the entire weight of the filler.

In one embodiment of the present invention, the filler is selected from the list consisting of calcium carbonate, preferably ground calcium carbonate (GCC), dolomite, which means a mixture of predominantly calcium and magnesium carbonate, and precipitated (precipitated) calcium carbonate ("precipitated calcium carbonate", PCC).

In one embodiment of the present invention, the filler is a precipitated filler. Preferably the precipitated or precipitated filler has a very small particle size, preferably a d50 of at most 1 µm, more preferably at most 500 nm, even more preferably at most 200 nm, still more preferably at most 100 nm and still more preferably at most 80 nm.

In one embodiment of the present invention, the filler is coated. The inventors have found that coated versions of fillers contain less moisture at the end of their production, and also have less tendency to absorb moisture after their production, such as during storage, transfer or transport. The inventors have also found that coated fillers can have a reinforcing effect on the end product, so that they can positively influence the mechanical properties of the end product. For example, the inventors have found that coated filler types can offer a higher "Fmax" to the end product. By Fmax is meant the highest tensile strength that is measured during a tensile test. The sample yields beyond the Fmax point on the tensile curve. sometimes referred to as the "tensile strength at break", although breakage does not necessarily occur with sealants. The inventors have found that this effect on the mechanical properties of the kit is more pronounced with precipitated fillers, such as with coated PCC. The inventors have also found that this beneficial effect is more noticeable with hybrid systems, which, as explained above, are SMP-based systems.

The inventors have found that when using coated fillers, the amount of thickener can be reduced to obtain a product with an equivalent rheology. Under certain circumstances, such as with coated PCC, a suitable paste can even be obtained without the use of a thickener.

In one embodiment, the present invention provides a method of manufacturing a product that can cure under the influence of moisture, wherein at least a portion of the ingredients are introduced into a mixing tub and mixed with, in the mixing tub, also to the extent necessary. reacting to each other, and wherein at least during a part of the method the mixing tank with contents is placed under vacuum, wherein the mixing tank is provided with an outlet mouth, and wherein the outlet mouth is closed by means of a plastic film.

The inventors have found that a plastic film as an additional sealing element can achieve a much better seal for the underpressure in the mixing bowl than alternatives such as only a rubber sealing ring and / or a shut-off valve, so that there is less risk that under the influence of the underpressure in the mixing vessel enters ambient air, and therefore moisture, through the outlet mouth into the mixing vessel and causes premature curing of the moisture-sensitive content of the mixing vessel.

The outlet mouth is preferably further closed with a lid, preferably a screw-on lid, the lid preferably also being sealed with a sealing ring, preferably a rubber sealing ring. The inventors have found that the plastic film appropriately avoids prolonged direct contact between the sealing ring and the contents of the mixing tub, which reduces the risk of chemical damage to the sealing ring, as well as simplifies cleaning of the sealing ring and of the lid that the outlet mouth close.

In one embodiment, to remove the mixed and reacted end product from the mixing tub, the plastic film closing the outlet mouth is removed or punctured. The puncturing preferably takes place through a suitable drain valve with which the outlet mouth is connected and with which the mixing tub is connected to the filling installation to fill and package the contents of the mixing tub. This feature brings the advantage that the possibility for the product in the mixing bowl to contact with moisture, and the time in which this contact would be possible, are considerably reduced via the outlet mouth.

In one embodiment, the plastic film consists of a thermoplastic and the thermoplastic film is thermally welded, as a membrane, on the outlet nozzle or preferably on an additional plastic adapter mounted on the outlet nozzle, and preferably this adapter is screwed onto the outlet nozzle . The film is preferably made from polyethylene (PE). The inventors have found that a welded foil provides a better seal than possible alternatives such as gluing or the use of an additional rubber seal. The welded film is also simpler and more economical because no additional elements are needed to realize the seal, although the step of welding is an additional step in the entire process. The application of the plastic film to an additional intermediate piece gives the advantage that the whole of the intermediate piece with the applied plastic foil can be prepared separately, and then quickly and easily applied to the outlet mouth, such as screwed, before the cover - with sealing ring - is applied. The membrane offers the additional advantage that it can even replace the shut-off valve during mixing. After all, the use of faucets involves the risk that the faucet has mechanical parts that are not, in themselves or in cooperation with other parts, really vacuum-tight.

In one embodiment, the present invention provides a method for manufacturing a moisture-curable product that utilizes a mixing tub for the production of the prepolymer by the reaction of a reactive polymer with a crosslinker, wherein closing the mixing vessel and introducing at least one liquid reagent for the reaction or another liquid ingredient of the formulation, the contents of the mixing vessel are stirred and the mixing vessel is further placed under a negative pressure, the negative pressure at most 0.50 bar absolute (bara) is preferably at most 0.40 bara, more preferably at most 0.30 bara and even more preferably at most 0.20 bara, preferably at most 0.15 bara, more preferably at most 0.10 bara, even more preferably at most 0.05 bara, preferably at most 0.03 bara, more preferably at most 0.02 bara and even more preferably at most 0.01 bara.

The inventors have found that placing the closed mixing vessel under reduced pressure is a quick and convenient way to remove a large part of the remaining air from the mixing vessel, with the humidity contained therein, so that this amount of moisture cannot react with any end product that may have remained in the mixing bowl after the previous production batch, which could harden that end product and form unwanted sheets. Stirring the contents of the mixing bowl during the vacuum period ensures homogenization of the contents of the mixing bowl and also a smooth reduction of any moisture that might still be dissolved in the liquid in the mixing bowl, because the concentration of dissolved moisture can therefore endeavor to remain balanced over the entire liquid content with the low vapor pressure of water in the gas phase above the liquid level. For this reason, the effect of this characteristic is more pronounced as the negative pressure is set lower, within the possibilities of the installation or equipment. Preferably the installation is able to achieve the prescribed underpressure, but it is not necessary to be able to go lower than at least 0.001 bara or 1 mbar absolute, preferably at least 0.010 bara, more preferably at least 0.025 bara and at even more preferably at least 0.050 bara. This brings the advantage that the installation which must provide for the underpressure must comprise fewer steps in series and can therefore be carried out more easily.

The inventors prefer to reduce the underpressure to the prescribed value as soon as practicable after closing the mixing tank. For example, the inventors prefer to achieve an underpressure of at most 0.40 bara within 60 seconds after the mixing bowl is closed, preferably within 45 seconds, more preferably within the first 30 seconds.

The inventors prefer to achieve an underpressure of at most 0.20 bara within a time span of 120 seconds, preferably within 90 seconds, and more preferably within 60 seconds. The inventors have found that this method ensures in a sufficient and feasible manner that as little moisture as possible can react with the end product in the mixing vessel that remained from the previous production batch.

In an embodiment of the present invention, the mixing tub is closed by joining the mixing tub and the lid, characterized in that a sealing ring is placed between mixing tub and lid, and that the material of the sealing ring has a Shore A hardness according to ASTM D2240 of at least 30 and at most 80, preferably at least 50. The inventors have found that a sealing ring with these characteristics can give a good seal with careful use and this over a long period of time during which the same sealing ring can be reused several times. The inventors have also found that the risk of damage is less during ring manipulation, both during use and when cleaning between two uses.

Preferably, the sealing ring material exhibits good resistance not only to the ingredients of the kit, but also to all intermediates and to the end product. The inventors have found experimentally that silicone rubber, polytetrafluoroethylene (PTFE), polypropylene (PP), polyethylene (PE), ethylene / propylene / diene monomeric plastic (EPDM) may be suitable candidates.

Preferably, however, a sealing ring is used that is formed from a compound that is a mixture of polypropylene (PP) with ethylene / propylene / diene monomeric plastic (EPDM). The inventors have found that the latter composition gives good chemical resistance, in particular to the extenders and solvents used.

In an embodiment of the present invention, the mixing bowl lid includes an inspection window and the mixing tube includes an outlet mouth that was temporarily sealed with a lid, and the method includes visual inspection by the inspection window of whether air bubbles are coming out of the liquid and whether air bubbles are coming from of a leaking lid on the outlet mouth, characterized in that an elastic sleeve, preferably a latex glove, is pulled over the lid on the outlet mouth and its connection to the outlet mouth.

The inventors have found that covering the lid, and its connection with the outlet mouth, can be done very simply and quickly with an elastic sleeve, and that this intervention is usually sufficient to stop ambient air from entering the mixing mouth into the mixing bowl. . This avoids a more extensive intervention in which the mixing tub must be replaced by transferring the contents of the mixing tub with the lid not properly closed on the outlet mouth to an empty, preferably thoroughly cleaned, second mixing tub. This more extensive intervention increases the risk of moisture contact between reactive residual material that would be present in the contents of the mixing vessel, and thus the possible formation of undesired sheets. This procedure can be inserted as a standard procedure, but can be reserved in case a problem occurs in achieving the set and desired vacuum, whereby the desired value can be achieved easier and faster without other and more cumbersome measures.

In an embodiment of the present invention, after homogeneously stirring the liquid in the mixing vessel, with the reactive polymer contained therein, and also after venting the closed mixing vessel by placing it under an underpressure, adding it to the mixing vessel of a cross-linker or cross-linker to react with the reactive end groups of the reactive polymer and thereby form the prepolymer and possibly additionally adding an extender to the contents of the mixing tub, characterized in that the mixing tub before and preferably also during adding the crosslinker is placed under an overpressure, preferably at an overpressure of at least 0.1 barg, more preferably at least 0.2 barg, and even more preferably an overpressure of at least 0.3 barg.

The inventors have found that placing the mixing tub under an overpressure before, and preferably also during, the addition of the crosslinker brings the advantage that the risk of loss of crosslinker in the gas phase, as well as the amount of crosslinker that can be lost through the gas phase. This means that more of the added amount of cross-linking agent is used efficiently, and therefore less excess can be added. Since the cross-linking agent is a reactive agent, this feature also brings the advantage that fewer problems occur caused by cross-linking agent that enters the exhaust installation.

In case at least one of the ingredients of the composition, for example a filler, is supplied by means of pneumatic transport, this excess pressure is preferably achieved by adding at least one of the gases used for that pneumatic transport. It should be noted here that a wide range of gases can be used in this context. However, the inventors' preference is for non-combustible gases such as nitrogen or air. Preferably, however, the inventors use dried or dry air to achieve this excess pressure, for the reasons stated elsewhere in this document.

The crosslinker can be added by pouring a pre-measured amount of it through an open manhole or peephole in the lid into the mixing bowl. In this case, according to the present invention, the slight overpressure is set on the mixing tub, and it falls back to atmospheric pressure when the manhole or peephole is opened to add the crosslinker. After adding the cross-linking agent, the mixing bowl is then closed again.

The crosslinker can be pumped into the mixing tub in an alternative embodiment. In this case, the mixing tub does not have to be opened, and according to the present invention, a slight excess pressure is preferably set on the mixing tub not only but also during the addition of the crosslinker.

When the cross-linker is then incorporated into the remainder of the liquid content of the mixing vessel, and the reaction is started, the inventors prefer to set an underpressure during the reaction of the cross-linker with the reactive polymer, i.e. in the closed mixing vessel. This underpressure is preferably at most 0.50 bar absolute (bara), preferably at most 0.40 bara, more preferably at most 0.30 bara and even more preferably at most 0.30 bara, preferably at most 0.15 bara, more preferably at most 0.10 bara, even more preferably at most 0.05 bara, preferably at most 0.03 bara, more preferably at most 0.02 bara and even more preferably at most 0.01 bara. For reasons explained elsewhere in this document, this negative pressure is at least 0.001 bara or 1 mbar absolute, preferably at least 0.010 bara, more preferably at least 0.025 bara and even more preferably at least 0.050 bara.

The inventors have found that the cross-linker or cross-linker is more expensive and volatile than the reactive polymer. Adding the crosslinker in a mixing tank that is placed under an overpressure, instead of in a mixing tank that is placed under an underpressure, reduces the risk of crosslinker or extender, especially if the latter is rather volatile and if present , is sucked into the vacuum installation that causes the temporary underpressure in the mixing bowl, would be lost and could lead to problems in the vacuum installation and the pipes leading to it. Another problem that is avoided is that the volatile cross-linker that has gotten into the liquid would evaporate due to the underpressure, which could cause the liquid volume to increase rapidly and to a large extent, and which could cause liquid to get to the inside of the lid of the mixing vessel which is then less able to participate in the reaction to form the prepolymer. Moreover, any loss of the composition to cross-linker means a loss of shelf life of the composition. The present invention therefore also contributes to achieving and / or maintaining the desired shelf life or shelf life of the composition.

The method according to the present invention means that the underpressure in the closed mixing tub, which is sometimes called "the vacuum," must be broken by admitting a gas into the mixing tub. In one embodiment of the present invention, dried air is admitted into the mixing vessel, preferably an air having a dew point of at most -40 ° C, preferably at most -45 ° C, more preferably a dew point of at most -50 ° C.

The inventors have found that the use of dried air to reduce the pressure in the mixing tub from the underpressure during the earlier phase of the production batch to the slight overpressure during the addition of the crosslinker offers the advantage of a higher safety compared to others gases that could be used to increase the pressure in the mixing bowl without bringing moisture into the mixing bowl. The exposure of operating personnel to dried air involves fewer safety risks than to other gases such as nitrogen or natural gas, because the dried air still contains sufficient oxygen so that there is no risk of oxygen insufficiency, and because the dried air does not in itself represent a fire risk .

After adding the cross-linking agent to the reactive polymer in the mixing vessel, the inventors prefer to disperse the cross-linking agent in the contents of the mixing vessel for a short time. During the dispersion, the inventors prefer to maintain a slight overpressure in the mixing tub in the range of 0.05-0.30 barg, preferably at least 0.08 barg and / or at most 0.20 barg, with more preferably about 0.10 barg. In this way, the inventors avoid the risk that part of the crosslinker would evaporate and could not participate in the reaction. After this dispersion, the inventors preferably maintain a reaction time, more preferably also a vacuum being re-established in the mixing vessel, preferably an underpressure as described above.

In an embodiment of the present invention, the stirring speed of the stirrer in the mixing vessel during the reaction of the crosslinker with the reactive polymer is limited to at most 300 rotations per minute (= rpm), preferably at most 150 rpm.

The limitation of the stirring speed during the reaction reduces the risk of liquid splashing. The splashing liquid can adhere to the inside of the mixing bowl cover, so that that portion of the liquid does not leave the mixing bowl when it is emptied through the outlet mouth. As a result, she is lost for the batch that is in production. In addition, it remains in the lid when the lid is removed from the mixing tub, whereupon it can react with moisture and start curing, giving rise to the formation of unwanted sheets. Therefore, by reducing the stirring speed during the reaction, the risk of skin formation is ultimately reduced. An additional advantage is that energy is also saved by the reduced stirring speed. An additional advantage is that the heating of the contents of the mixing bowl caused by the action of the shear or shear forces on the liquid is less high.

In an embodiment of the present invention, after mixing of the cross-linking agent, and preferably after dispersing of the cross-linking agent in the liquid, the mixing vessel is again placed under reduced pressure. The reduced pressure is preferably at most 0.5 bar absolute (bara), more preferably 0.3 bara, even more preferably 0.2 bara.

The inventors have found that this reduction in the pressure in the mixing tub, by evacuation from the gas phase in the mixing tub, removes even more moisture from the reacting mixture in the mixing tub. This moisture may have entered through the manhole or any other opening in the mixing tub or in the lid, a manhole normally provided in the lid of the mixing tub, which had to be opened to allow the addition of the crosslinker. Preferably the crosslinker is added as an amount of liquid that is first accurately measured and then added to the contents of the mixing tub. If, for this purpose, the liquid or the contents of the mixing bowl must come into contact with the ambient air, it is preferable to work quickly to reduce the length of this exposure.

In one embodiment, the present invention provides a process for producing a product which can cure under the influence of moisture, which runs in batches and which uses a mixing vessel for the production of the prepolymer, wherein after obtaining the prepolymer in the mixing bowl the lid of the mixing bowl is lifted and the stirrer and / or scraper is retrieved from the liquid, the mixing bowl is closed by means of two sheets of plastic (plastic) foil, the first sheet being applied to the product as well as possible and against the upright wall of the opened mixing tub, and a second sheet afterwards is stretched over the top edge of the mixing tub.

The first sheet seals the product in the mixing tub as well as possible from contact with the air above the first sheet, while the second sheet seals the mixing tub, and especially the amount of air in it, above the first sheet, from the air above and around the mixing bowl. The inventors have found that this double seal, with the aid of the two correctly applied plastic films, provides a highly effective seal to protect the water-sensitive prepolymer in the mixing bowl from moisture contact and thus to prevent premature curing, during removal of the filled mixing bowl from underneath it. retrieved lid, usually with the agitator and / or scraper attached to that lid, and during the transfer of the full mixing tub to the filling installation and the connection thereto.

In one embodiment of the present invention, the retrieved stirrer and / or scraper is scraped off, preferably manually with a suitable knife, and the scraped product is dropped into the mixing tub before the mixing tub is sealed with the plastic films.

This offers the advantage that less product remains on the stirrer and / or scraper, which can come into contact with ambient air and therefore with the moisture therein, before a new mixing tub is provided under the lid and that mixing tub can be closed with the lid. This reduces the amount of the product from the previous production batch that remains and mixes with the ingredients of the next production batch. Since these ingredients can still contain water, and the remaining product is very reactive and provided that contact with moisture starts to harden, the scraper of the stirrer and / or scraper reduces the formation of unwanted sheets in the next production batch.

In an embodiment of the present invention, the inside of the lid is not scraped off.

This offers the advantage that this material, which is collected against the inside of the lid, and which therefore has had much more time and chance of already reacting with moisture, such as from the ambient air that is sometimes present in the mixing vessel, is not released. mixed into the finished product in the mixing tub. This reduces the chance that a partially reacted product already occurs in the finished product, which leads to the formation of annoying "sheets".

The inventors prefer that this material, which collects against the inside of the mixing bowl lid during production, is removed and disposed of separately from the quality product that is manufactured and obtained in the mixing bowl. This material may be removed and packaged as an inferior but still usable product, but is preferably disposed of as unusable and waste product.

In another embodiment of the present invention, the retrieved stirrer and / or scraper is not scraped off before the lid is replaced on a new mixing vessel. This material is preferably used as recovery material for the next production step with the same stirrer and / or scraper.

This offers the advantage that less time is required to remove the mixing bowl with the finished composition and bring it to the next processing step. This gives the finished product in the mixing tub less time to come into contact with the ambient air and with the moisture it contains.

In an embodiment of the present invention, an amount of desiccant is provided between the two plastic films. The desiccant absorbs moisture from the amount of air between the two plastic films, so that less moisture can find its way to the product in the mixing bowl under the first film. This offers the advantage that the risk of premature curing of the product in the mixing tub is reduced before the product can be filled in the filling installation.

According to the inventors, suitable drying agents are silica gel or molecular sieves.

In an embodiment of the present invention, the ambient air between the two plastic films is at least partially replaced by a dry gas, preferably nitrogen or dried air, more preferably by dried air, which preferably has a dew point of at most -40 ° C, preferably at most -45 ° C, more preferably a dew point of at most -50 ° C.

In one embodiment, the present invention provides a method for manufacturing a product that can cure under the influence of moisture, which method proceeds in batch and which uses a mixing vessel for the production of the prepolymer, characterized in that the reactive polymer and the crosslinker, as well as the additional ingredients required for the production step in the mixing bowl, are introduced into the closed mixing bowl and react without opening the mixing bowl, and the mixing is done without opening the mixing bowl, and the product is also removed from the mixing bowl without opening the mixing bowl.

The provision that both the raw materials for the production of the product can be fed into the mixing bowl and the product can be removed from the mixing bowl without having to open the mixing bowl offers the advantage that the risk of contact with ambient air and with the moisture contained therein is reduced for the moisture sensitive ingredients, for the reacting reaction mixture, as well as for the moisture sensitive product formed by the reaction of the reactive polymer and the cross-linker. This advantage is achieved without losing the flexibility advantage offered by a batch production process compared to a continuous production process. Continuous production processes are suitable for manufacturing large quantities of a relatively small number of products. With batch production processes, it is always possible to adjust or change the formulation and the ingredients, so that a different product can always be obtained. The advantage of this invention can therefore be seen in comparison with a batch production method in which the mixing tub must be opened to either add one of the ingredients to the mixing tub or to be able to remove the end product from the mixing tub.

The advantage obtained with the present invention is especially important with regard to the amount of reaction product that remains in the mixing tub after removal of the reaction product from the mixing tub. Thanks to the present invention, that amount of residual reaction product does not get a chance to react with moisture from ambient air, because the mixing tub remains closed between successive production batches. This residual reaction product mixes with the ingredients of the next batch, but due to the lack of any important moisture entering between two production batches, this reaction product has not had a chance to cure already, which would otherwise often lead to the formation of sheets or "flakes." Thus, the present invention considerably reduces the risk of skin formation compared to the production batch with a mixing tub that must be opened each time to add certain ingredients and / or to remove the product from the mixing tub. remove.

This invention brings the important advantage that no or very little less usable or unusable product remains, which can be regarded as waste product.

An additional advantage is that the production also requires less human intervention, such as to remove the opened mixing tub with the finished product from under the lid with stirrer and / or scraper, as with the typical batch process. This invention allows an operator to operate multiple mixers, while for a smooth and smooth progress of a typical batch process, multiple operators are required for one mixer.

A further advantage of this invention is that the method can be highly automated, which greatly reduces the risk of human error, and thus increases the reliability of production, especially in terms of time planning and product quality.

In an embodiment of the present invention, the mixing tub is closed with a lid and the lid of the mixing tub is provided with a height-adjustable stirring system such that, without having to open the mixing tub by raising the lid, the height adjustment of the stirrer can be adjusted relative to the liquid level in the mixing bowl.

The inventors have found that during the entire production course of the batch production of the product in the mixing vessel, the liquid level can change considerably. For example, adding the necessary amount of the ingredient that has to make a paste of the liquid reaction product causes a considerable increase in volume and thus a substantial increase in the liquid level in the mixing vessel. This feature of the present invention offers the advantage that the height of the stirrer can be adjusted each time as a function of what is desired in each step throughout the course of production such as with regard to stirring effects, splashing or prevention thereof, as well as with regard to the energy contribution, which usually also determines the temperature rise caused by the action of the shear forces or shear forces during stirring.

In one embodiment of the present invention, the mixing tub is kept under vacuum during the addition of the reactive polymer and the cross-linker, preferably also during the addition of the plasticizer and / or the extender, if applicable.

Keeping the mixing bowl under pressure while adding the ingredients offers the advantage that any remaining end product from the previous batch during the introduction of the ingredients has as little chance and time as possible to react with any moisture that would come with these ingredients . This feature of the present invention thus reduces the risk of forming unwanted sheets or "flakes" of already fully or partially cured prepolymer in the mixing vessel, for example during the preparation of the reaction or during the formation of the prepolymer.

In one embodiment of the present invention, a thickener is added to the mixing tub and the mixing tub is maintained at approximately atmospheric pressure during the addition of the thickener, and, if a negative pressure prevails in the mixing tub, this negative pressure is broken prior to adding the thickening agent .

The inventors preferably use silica (SiO 2) as a thickener because of its exceptional reinforcing effect. Various forms of silica can be used as a thickener, including "precipitated silica", but the inventors prefer to use the so-called pyrogenic silica, because this reinforcing effect of the thickener is even more pronounced. The silica is thereby preferably supplied in solid form, as powder or flakes, however, this solid form of silica is characterized by a very low bulk density, so the ingredient is very light and very susceptible to being carried in a moving stream of gas or air. silica would easily find its way into the suction system responsible for the underpressure in the mixing bowl, if this suction system is operated during the addition of the silica to the mixing bowl, therefore the inventors prefer to connect the suction system to the mixing bowl before starting to add it silica, and also to re-open this compound only after adding the desired amount of silica to the mixing tub. During the addition of the silica, the applicants preferably maintain a slight overpressure in the mixing vessel. This excess pressure is preferably provided via the supply line through which the silica is added. This excess pressure is then preferably released afterwards via the weighing installation where the correct dosage of the silica is provided, so that the surplus gas, preferably dry air, can escape via the filter provided on that weighing installation.

In an embodiment of the present invention, a thickener is added to the mixing tub, preferably silica, and the thickener is introduced into the mixing tub in a pneumatic manner. The inventors have found that pneumatic transport is a very convenient way to transport the light but solid thickener in a gas stream, and that at the same time the added gas can be used to break the underpressure that is preferably maintained during the reaction at the time that it is thickener is added. The inventors preferably use a stream of air for the pneumatic transport, and more preferably a stream of dried air. More preferably, this dried air has a dew point of at most -40 ° C, preferably at most -45 ° C, more preferably a dew point of at most -50 ° C.

The use of air offers the advantage of a reduced risk or increased safety towards the treatment personnel, because air is not flammable when escaping into the atmosphere, which would be the case with the use of a flammable gas such as natural gas, and because air does not dilute the oxygen content in that atmosphere in the vicinity of the point of escape when escaping into the atmosphere, as well as when left in a container does not represent an environment in which an unsuspecting operator would suddenly fall into oxygen deficiency, which would be the case with the use of nitrogen.

In one embodiment of the present invention, the mixing tub is kept under vacuum during pumping out of the product from the mixing tub.

The inventors prefer to also maintain the underpressure in the mixing tub during the emptying of the mixing tub, in order to also reduce the risk of moisture contact during that part of the production process.

In an embodiment of the present invention, the arms of the stirrer in the mixing vessel are provided with scrapers that reach a distance of at most 5 mm from the side walls of the mixing vessel, preferably at most 4 mm, more preferably at most 3 mm and even more preferably at most 2 mm.

The inventors have found that this design of the stirring system, in conjunction with the height-adjustability of the stirring system, offers the possibility of scraping the inside of the side walls of the mixing bowl properly while emptying the mixing bowl, and therefore little or no residual product remains against the side walls of the mixing bowl when the mixing bowl is emptied.

In an embodiment of the present invention, the bottom of the stirrer has substantially the same shape as the bottom of the mixing bowl, preferably with a tolerance of at most 5 mm, more preferably at most 4 mm, even more preferably at most 3 mm and most preferably at most 2 mm. Preferably, the bottom of the mixing tub is flat, and the bottom of the stirrer is also in the same plane.

This brings the advantage that the bottom of the mixing tub is also properly scraped off, so that less residual product remains after emptying a finished mixing tub.

In the embodiment of the present invention in which the bottom of the stirrer has substantially the same shape as the bottom of the mixing vessel, the bottom of the stirrer is additionally provided with a rubber strip over substantially the entire width.

This brings the advantage that the bottom of the mixing bowl is scraped off even better, so that less residual product remains after pumping out a finished mixing bowl.

These provisions of scrapers on the stirrer, of close cooperation between stirrer and mixing bowl bottom, and of the additional rubber strip, each individually and even more by their cooperation offer the advantage that there is little so-called "cross-contamination" or cross-disturbance between the products of successive production batches. An additional advantage is that when it is nevertheless necessary to open the mixing bowl and clean it, little waste is released during the cleaning, thereby reducing waste production from the production process. The inventors have found that a batch process with a mixing tub that is at least partially filled before the lid is closed, as well as having to be opened to bring and mix the mixing tub full of end product to the filling plant is usually characterized by about 2% production waste . The inventors have determined that the production waste can be reduced to less than 0.5% of the total production turnover.

In one embodiment of the present invention at least one upwardly projecting protrusion is provided on each of the two arms of the stirrer, which protrudes into a point with an angle of at most 45 degrees, which corresponds to at most an eighth circle. The two arms are preferably each provided with at least two such protrusions, more preferably at least four, even more preferably at least six, preferably at least eight, more preferably at least twelve and even more preferably at least 14 upward pointed pointed protrusions.

These pointed protrusions preferably have a point angle of at most 30 degrees.

The inventors have found that the upwardly directed pointed protrusions on the arms of the stirrer contribute greatly to a good and rapid dispersion of powders in the liquid content of the mixing vessel. This is especially advantageous when dispersing the thickener. The protrusions ensure the rapid disappearance of so-called "dots" ("grains") that form easily when adding the thickener to the mixing bowl.

In the embodiment of the present invention with the upwardly pointed pointed protrusions on the stirrer arms, these protrusions are provided on the outer 60% of the stirrer arm, preferably on the outer 50%, more preferably on the outer 40%, and even more preferably on the outer 30% of the stirrer arm. This brings the advantage that for the same stirring speed, the tip speed of the pointed protrusions is higher, which has a favorable effect on the speed with which a powder such as the thickening agent can be dispersed in the contents of the mixing vessel.

In one embodiment of the present invention at least one upwardly directed blade is provided on each of the stirrer's arms, which blade forms an angle with the longitudinal axis of the stirrer arm that is less than 90 degrees or a quarter circle. Preferably the angle between the blade and the longitudinal axis of the stirrer arm is at most 60 °, more preferably at most 45 °, even more preferably at most 30 °.

The inventors have found that the blades on the stirring arms provide a central vortex when stirring, so that a powder gets into the contents of the mixing tub much faster. The inventors have also found that this effect is stronger as the blade makes a smaller angle with the longitudinal axis of the stirrer arm.

These blades are preferably provided on the inner 50% of the stirrer arm, preferably on the inner 40% of the stirrer arm. Nevertheless, the inventors prefer not to bring those paddles closer to the stirrer axis than 20% of the length of the stirrer arm. The inventors have found that this promotes a good vortex and, as a result, intense internal fluid circulation arises from the center of the mixing bowl towards the outside, then upwards along the walls, bending inwards at the top, and then more centrally back to to come down and carry added powder in its flow.

In an embodiment of the present invention, several of the different ingredients are added to the mixing tub simultaneously, and this while the stirrer has already been operated.

By feeding different ingredients in parallel to the mixing bowl instead of one after the other, such as the reactive polymer, the plasticizer and the possible extender, and by meanwhile already stirring the liquid in the mixing bowl, a large time saving is achieved in the overall production trend, always in comparison with a conventional batch procedure in which the ingredients are successively introduced into an open mixing vessel and where stirring can only take place when the lid with stirrer is placed on the mixing vessel, the mixing vessel can therefore be closed and the pressure can be lowered and only then remove as much air and moisture as possible from the gas phase at the top of the mixing bowl as well as the air and moisture that may have been dissolved in the liquid ingredients introduced.

In one embodiment of the present invention, the product is pumped from the mixing tub to a buffer tank before the product is filled into its final package.

The inventors have found that the use of a buffer tank allows the mixing tank to be emptied quickly so that it becomes available for a subsequent production batch. The use of multiple buffer tanks also makes it possible to produce an extensive production range with greater flexibility on the same mixing tub or mixing machine. Thus, thanks to several buffer tanks in the same mixing vessel, it is relatively easy to switch between the successive production of two end products with the same color but with different viscosities, either with different plasticizers or a difference in plasticizer content, or with different extenders or a difference in extender content, or with different filler or with a difference in filler content. Even switching from a batch of a transparent end product to the next batch of a colored end product or a product with filler can be made quite easily without many special interventions thanks to the buffer tanks. The use of buffer tanks together with the closed mixing tank therefore offers the advantage that it is possible to proceed to a subsequent production batch much sooner after a previous production batch, which can considerably increase the production turnover or production capacity of the mixing tank.

In the embodiment of the present invention that uses a buffer tank to receive the product from the mixing tank, the product is pumped out of the buffer tank and pigment and / or fungicide is mixed into the product downstream of the buffer tank before the product is filled in its final packaging.

The mixing of pigment and / or fungicide in the product on its route to the filling plant makes it possible to produce a wide range of different end products with a few basic products, which may, for example, still differ in their plasticizer, extender and / or filler content. able to produce and fill in their final packaging.

The pumping of product from the buffer tank to the filling installation is preferably done with a piston pump. A static mixer is preferably used when mixing the pigment and / or the fungicide.

In the embodiment of the present invention that uses a buffer tank to receive the product from the mixing tank, the product in the buffer tank is a transparent product, i.e., a product without filler, and the product is pumped out of the buffer tank and is discharged downstream of the buffer tank is mixed into the product in the desired amount of filler, before the product is filled in its final packaging.

The mixing of the filler into the product on its route to the filling plant makes it possible to produce and fill a number of different end products with the same transparent basic product. These products can then differ in the choice and quantity of filler.

The addition or not of the filler to the product on its way from the buffer tank to the filling is preferably combined with the mixing of pigment and / or fungicide in a similar way, that is also to the product on its way from the buffer tank to the filling.

In an embodiment of the present invention, at least one, and preferably all, of the liquid ingredients of the production procedure are stored in separate feed tanks in which the atmosphere above the liquid consists of dried air prior to their transfer to the mixing tub. Preferably, the dried air added to that feed tank has a dew point of at most -40 ° C, preferably at most -45 ° C, more preferably a dew point of at most -50 ° C.

This feature brings the advantage that the liquid ingredients of the production batch or production procedure are less likely to absorb moisture undesirably before being introduced into the mixing tub. This implies that less moisture must be removed from the mixing tub to prevent this moisture from leading to premature curing of the formed end product and also of any end product from the previous production batch left in the mixing tub and on the stirrer after insertion of the ingredients for the new production batch.

In an embodiment of the present invention, the reactive polymer and the crosslinker are premixed on the way to the mixing tub.

This offers the advantage that the cross-linker and the reactive polymer are already at least partially mixed with each other before they end up in the mixing vessel, so that they can already react with each other and even less additional time is required for further mixing between these two reagents, and / or for the further reaction of these two reagents to form the intended product which can cure under the influence of moisture. This feature further offers the advantage that the reaction occurs between the two reagents without any dilution by another and non-reactive ingredient, such as the plasticizer and / or the extender. By allowing this reaction to proceed undiluted, the reaction rate is also increased compared to the conventional method where the reaction proceeds in the presence of an amount of plasticizer and / or extender.

This pre-mixing is preferably carried out with the aid of a static or dynamic mixer, more preferably a dynamic mixer which is characterized by a specific lead time. A dynamic mixer is a mixer in which external energy can be added to the mixing mixture by exerting shear or shear forces on it. Preferably, the shear forces are also adjustable and adjustable. The inventors prefer a dynamic mixer in comparison with a static mixer because they found that the pressure drop across the mixer itself is also lower, so that the feed-through requires less energy.The applicants prefer to use the Dynamic Inline Mixer Type DLM / S-330 offered by INDAG Maschinenbau GmbH (DE).

The inventors prefer to carry out pre-mixing before the reactive polymer / crosslinker mixture is stored for some time in a buffer tank upstream of the mixing tub.

This feature offers the further advantage that more can be saved on the reaction time that might be needed in the mixing tank itself. Preferably, the prepolymer is predominantly and more preferably fully reacted before it enters the mixing vessel, so that no additional time is to be provided in the mixing vessel to complete the reaction.

In the embodiment of the present invention wherein the reactive polymer and the crosslinker are premixed to an at least partially grafted prepolymer before this prepolymer is fed to the mixing tub, the at least partially grafted prepolymer is fed to the mixing tub from below. The inventors prefer that the reaction between the reactive polymer and the cross-linker has already been completed as completely as practically possible before the prepolymer reaches the mixing vessel.

Usually ingredients are introduced into the mixing tub through an opening in the lid or the top wall of the mixing tub. This feature of the present invention offers the advantage, in comparison with that conventional feeding method along an opening in the top wall of the mixing vessel, that there is much less risk of splashing of this grafted polymer, which can adhere to the top of the equipment such as the inside of the lid or the upper part of the stirrer. Encapsulated prepolymer that has adhered to those sites can incorporate a portion of it when introducing the thickener that is light and easily clouded up, whereby that encapsulated prepolymer quickly rises to a paste and therefore can no longer drain and fall back into the liquid in the liquid. mixing tub. As a result, the amount of residual product that remains in the mixing tub from the previous to the next production batch would increase the so-called "cross-contamination". Thus, the feature of the present invention referred to here greatly reduces the amount of cross-contamination between successive production batches, as well as the amount of residual product that remains when opening the mixing bowl for cleaning, and which must therefore be disposed of primarily as waste.

In an embodiment of the present invention, thickener is added to a space in which it is already at least partially, and preferably the fairly fully grafted, prepolymer is gradually fed by pressing the prepolymer through a narrow elongated opening or slot to form a liquid curtain.

This method of gradually thickening agent and the pre-encapsulated prepolymer offers the advantage that the curtain of prepolymer offers a large available surface area to receive thickener. This advantage is particularly pronounced when using silica as a thickener, especially in a form that is light and easily clouded up, such as in the form of powder or flakes. Due to the large surface area, the thickener easily and quickly finds its way into the liquid in which the prepolymer is contained and whose rheology has to be changed to form a paste.

This assembly can be done by pumping the encapsulated prepolymer from the mixing tub to the space where it is brought into contact with the thickener, whereupon the mixture is sent back to the mixing tub.

In the embodiment of the present invention in which the reactive polymer and the crosslinker are premixed, the thickener is added to the premixed, and preferably the grafted, prepolymer on its way to the mixing tub.

Preferably, an amount of solvent, solvent, extender and / or plasticizer is added to the prepolymer before adding the thickener.

The inventors have found that adding and acting in solvent, solvent, extender and / or plasticizer is much easier before the thickener is added than after, because the viscosity of the prepolymer without thickener is much lower than the same prepolymer in which an amount of thickener is present , which makes stirring to obtain good interference better and requires less energy. In addition, the inventors have found that less thickener is required to achieve a certain viscosity when the plasticizer and / or extender is added before the thickener as compared to an addition of the plasticizer and / or extender after the thickener.

In the embodiment of the present invention in which the thickener is added to the already at least partially encapsulated prepolymer, the blend of the additive passes through an intermediate mixer, preferably a dynamic intermediate mixer due to the above-cited advantages of controllability and lower pressure drop, such that the thickener is even better dispersed in the liquid with the prepolymer.

This feature offers the advantage that a good dispersion of the thickener in the liquid is obtained more quickly, so that the pressure in the mixing tank can also be reduced more quickly without increasing the risk that still undispersed thickener could be included in the suction system that was used for the underpressure. In this way, the following steps in the production procedure can also be brought forward, so that the overall residence time in the mixing vessel is reduced and a higher throughput can be achieved in the same mixing vessel.

In an embodiment of the present invention, an intermediate product without filler is produced in the mixing tub, which may then first be transferred to a buffer tank, and in that intermediate product the filler is only added on its way to the filling installation.

This feature offers the advantage that the same product from the mixing tub and / or the buffer tank offers the possibility of still manufacturing several products. In addition to the choice to add no, little or more filler to the same product from the mixing bowl, there is still the possibility of giving different colors to the same end product, or to adjust the amount of filler in the end product to the nature and quantity of the colorant or colorant mixture that one wants to use for a certain end product, or conversely to adjust the amount of colorant to the amount and nature of the filler.

Preferably, the inventors add the filler as a slurry or suspension of the filler in a carrier. This is particularly useful if the filler is added to the product on its way from the mixing tub to the filling installation. In this embodiment, suitable carriers are best selected from silicone oil or extender.

EXAMPLES

The following examples are worked out in more detail to illustrate the present invention. The examples describe the production and filling of the following silicone sealants in accordance with the following recipes:

Table 1

Example 1 (VB 1) forms a filled kit based on an oxime cross-linking agent. Example 2 (VB 2) produces a transparent kit based on an alkoxy crosslinker in the mixing tub. Example 3 (VB 3) is for a transparent kit with acetoxy-based crosslinker.

Polymer FD 80 and FD 120 were obtained from Wacker (DE). Polymer FD 80 and Silopren E80 had an average molecular weight of 70318 g / mol. Polymer FD 120 had a molecular weight of approximately 81418 g / mol. Silopren E80 and W100, and

Silopren W1000 were obtained from Momentive Performance Chemicals. Exxsol® D140 was obtained from ExxonMobil Chemical.

Vernetter ES23 had obtained ethyl triacetoxysilane from Wacker, which has a molecular weight of 234.28 g / mol. Vernetter LM43 was a mixture of mainly acetone-oxime and butane-2-one O, O ", O" - (methylsilylidyn) trioxime supplemented with a small amount of methyltrimethoxysilane. The crosslinker was obtained from the company Nitrochemie, and had an average molecular weight of 259.9 g / mol. The crosslinker Silopren TP 3625 was vinyl trimethoxysilane (VTMO) obtained from Momentive Performance Chemicals, and had a molecular weight of 148.23 g / mol.

Adhesive promoter ("Haftvermittler") DBS was di-tert-butoxy-diacetoxysilane, which was obtained from Wacker. Silquest A-1100 was 3-aminopropyltriethoxysilane obtained from Momentive Performance Materials. Silquest VX-225 was an amino-functional oligosiloxane obtained from Momentive Performance Materials.

Stabilizer Silopren TP 3626 was 2-ethylhexyl dihydrogen phosphate, obtained from the company Momentive Performance Chemicals. This compound is a good stabilizer for, for example, a tin catalyst, but is also active as a catalyst for the end-capping reaction, i.e. the reaction of the cross-linker with the reactive polymer.

Aerosil® 150 was a pyrogenic form of silicic acid obtained from Evonik and HDK® H15 was a pyrogenic form of silicic acid obtained from Wacker.

The Microdol A1 was a ground dolomite (Ca / Mg carbonate) obtained from OMYA AG. This product had a water content of +/- 600 ppm by weight, and was not coated.

The dibutyl tin diacetate was obtained from the company Momentive Performance Materials. The TIB KAT® 217 was a dioctyl tin oxide-based catalyst, obtained from TIB Chemicals. The Silopren TP 3560 was also a dioctyl tin-based catalyst, which was obtained from the Momentive Performance Materials company.

EXAMPLE 1: PRODUCTION OF A SILICONE KIT ON THE BASIS OF AN OXIME-CONTAINER

A clean mixing bowl on wheels was driven. A drain opening is provided at the bottom of the mixing bowl. This was closed by means of a screw-on lid, which was provided with a rubber sealing ring that must connect with the drain opening. A plastic film made of polyethylene was provided between the metal of the discharge opening and the lid with its rubber sealing ring, which prevents the seal from coming into prolonged and direct contact with the contents of the mixing bowl. This avoids possible chemical damage to the seal ring, and also avoids having to clean the lid with seal ring after each use.

For less viscous products than in this example, a piece of tube is preferably mounted on the outlet mouth of the discharge opening with an additional plastic film of a thermoplastic plastic such as polyethylene on its free end, the film being thermally welded on the free end and the hermetically sealed free end. The drain valve is then screwed onto the free end that is sealed as such. A drain valve is used as a drain valve, so that an operator can puncture the plastic film through the opened drain valve.

The clean mixing bowl was driven on a scale. In the open mixing tub, the prescribed quantities of the reactive polymer, of the plasticizer, and if required by the recipe, also of the extender, were loaded in succession based on the increase in the total weight of the mixing tub with its contents. If necessary, pigments and other ingredients other than crosslinkers, adhesion promoters and catalysts are now added. However, the amounts of these additional ingredients are much smaller than the total liquid content formed by the polymer with the plasticizer and the possible extender. The ingredients other than polymer, plasticizer and extender are therefore preferably introduced on the opposite side of the place where the outlet opening of the mixing tub is located. This brings the advantage that the risk is kept as small as possible that a significant part of one of these ingredients ends up in the outlet opening and would not be mixed well with the rest of the contents of the mixing tub.

The clean mixing bowl is driven under the lid with a stirrer. The lid is provided to connect with the mixing bowl to a sealing ring made from a silicone compound with a hardness of 60 Shore A and with a rectangular profile of 20x15 mm. The inventors have found that this material is sufficiently chemically resistant to the various ingredients as well as to those of the end product, and also has a correct combination of hardness and elasticity.

The lid is furthermore provided with a stirring system rotatable about a vertical axis, which hangs and protrudes below the lid. The stirring system mainly consists of at least one rotor, preferably two rotors, also called "dissolver", mounted at the bottom of a vertical axis. At least one mixing wing can be placed on the shaft at a height of your choice.

The lid with stirring system was placed on the mixing bowl. If it is visually determined through the peephole that a wing is not at the appropriate height relative to the liquid level in the mixing bowl, the lid is lifted again and the position of the wing on the shaft is adjusted. The mixing vessel was then closed by lowering the lid onto the mixing vessel.

The stirring system was activated to homogenize the contents of the mixing tub. At about the same time, the vacuum system was activated and an underpressure was set in the mixing tub of about 0.2 bara. The inspection window in the lid visually inspected that no gas bubbles were coming through the liquid, and that the outlet opening was therefore properly closed. If it is determined that the outlet opening is not properly closed, the operator pulls a latex glove over the lid on the outlet mouth, including its connection to the outlet mouth.

After the contents of the mixing tub were well mixed, the vacuum installation was stopped. The vacuum in the mixing tub was then broken and an overpressure was set of about 0.3 barg by introducing air under pressure that had a dew point of -50 ° C.

The correct amount of the crosslinker was weighed in advance and added slowly to the contents of the mixing tub while the stirrer remains on. The crosslinker was added through the manhole in the lid.

Before adding the cross-linking agent, the stirring speed was lowered to 150 rpm, and this stirring speed was later also maintained during the prescribed reaction time. After adding the cross-linking agent, the manhole was closed again and a negative pressure of 0.2 bara was again set in the mixing vessel until the end of the reaction time. To allow the cross-linker to react with the reactive polymer, the reaction is generally allowed to continue for a period of 10 minutes. Subsequently, the vacuum was again broken, using dried air with a dew point of -50 ° C, to an overpressure of approximately 0.3 barg. Stirring continued.

The prescribed amount of the thickener was then added through the re-opened manhole. This thickener can be added through the re-opened manhole, for example, by shaking bags in which the thickener was supplied. However, the inventors prefer to pneumatically add the thickener from a storage vessel with a diaphragm pump. In both cases, the inventors prefer not to set underpressure during the addition of the thickener. During the addition of the thickener, the volume in the mixing tub increased. By stirring, the thickener was dispersed throughout the contents of the mixing tub.

After dispersing the thickener, the prescribed amount of filler was added and mixed in, as well as the adhesive promoter. After the addition and during the mixing, a negative pressure of 0.2 bara was again set in the closed mixing bowl again and stirring continued until the contents of the mixing bowl became homogeneous and no dots ("grains") were present anymore, and preferably also no sheets ("flakes") were found in the mixing bowl contents.

As a final ingredient, the catalyst was added in a subsequent step, again through the opened manhole and after breaking the vacuum with dry air as explained above. Subsequently, an underpressure of approximately 0.2 bara was again set and further stirred. The vacuum, along with traces of moisture, also removes as much dissolved air from the product as possible, reducing the risk of gas bubbles forming during later production steps, during storage or when using the kit.

After this final mixing period, the vacuum was broken by admitting dry air with -50 ° C dew point. A sample was taken for standard quality control. After approval of the key features, the lid (with the attached stirrer) was lifted. Because the next production batch in this mixing installation was of the same quality, only the bottom of the scraper was scraped off with a scraping knife, whereby the scraping was collected in the full mixing vessel. The full mixing vessel was then driven away under the stirrer lid and a new, clean mixing vessel was driven underneath, preferably containing the required amounts of reactive polymer and plasticizer.

A first plastic sheet was then placed on the pasty content of the full mixing bowl and pressed against the product and with its edges against the walls above the product level. A second plastic sheet was then stretched over the mixing tub to close the top opening of the mixing tub. In the space between the two plastic sheets, if desired, such as in warm weather, a small amount of active drying agent can be provided in solid form.

The full mixing bowl was driven under the press of the filling installation and connected to it via the outlet mouth of the mixing bowl. The product was filled into plastic tubes that were sealed after filling by placing a head or plunger in the open end of the tubes. On the inside, where the plunger must come into contact with the sleeve, the plastic sleeve is pre-lubricated by providing a layer of a heavy hydrocarbon wax, preferably a wax that has been made more stable by hydrogenation against the influences of oxygen and / or UV radiation, a layer with preferably a thickness of approximately 0.10 mm. This wax can be applied in any way known to those skilled in the art. For example, the wax can be sprayed in molten form as a warm liquid, in solution in a lighter organic solvent, or as an emulsion in a carrier. Such an emulsion can even be water-based, the water evaporating fairly quickly and is no longer disturbing or even present to an extent that it would have an influence on the contents of the tube.

EXAMPLE 2: PRODUCTION OF A SILICONE KIT BASED ON ALKOXY CONTAINER

The same method was followed as in Example 1, with the following adjustments. This product must be transparent, and therefore no filler has been used. This formulation also contains a stabilizer. This was added after the cross-linking of the cross-linking agent, after which further mixing was continued for 3 minutes. After all, the selected stabilizer is itself active as a catalyst for the reaction between cross-linker and reactive polymer, so that it is preferably added to the mixing vessel as soon as possible after the cross-linker to shorten the reaction time. During each addition in each of the examples, a low stirring speed is preferably maintained to promote the action of the added ingredient.

EXAMPLE 3: PRODUCTION OF A SILICONE KIT BASED ON ACETOXY CONTAINER

An underpressure of approximately 0.2 bara was set in a closed mixing vessel. The mixing vessel is provided with a height-adjustable stirring system, the stirrer being provided with scrapers that reach a distance of at most 2 mm away from the side walls of the mixing vessel, and further provided with additional surfaces to cause more turbulence in the bulk of the liquid content of the mixing bowl.

In a buffer tank with weighing equipment, the prescribed amount of the reactive polymer was first weighed from a feed tank. The plasticizer, the extender and the crosslinker were also made available by offering them from food tanks. The feed tanks were kept continuously under an atmosphere of air with a dew point of -50 ° C.

The polymer from the buffer tank and the ingredients from the feed tanks, the latter under coriolis flow measurement to allow correct dosing, were simultaneously fed to the mixing tub under vacuum, and this while the stirrer is on.

After the reaction of the cross-linker with the reactive polymer, the vacuum was broken and a slight excess pressure of 0.05 barg was set, after which the prescribed amount of the thickener was added and dispersed in the liquid. The thickener was supplied pneumatically with as carrier a stream of air with a dew point of -50 ° C.

During the dispersion of the thickener, the mixing tub was again placed under a negative pressure of approximately 0.2 bara. After dispersing the thickener, the adhesive promoter and the catalyst were added and mixed in. After completing the mixing procedure, the mixing tub was emptied to a buffer tank by pumping, and this while maintaining the vacuum. During this emptying, the stirrer is used to roughly scrape the inner walls and the bottom of the mixing bowl.

Afterwards, the buffer tank is pressurized with the aid of a movable pressure plate provided in it and the contents of the buffer tank are pumped to the filling installation with a piston pump. On its way to the filling installation where the pasta is filled in its sales package, the filler, if desired in the form of a slurry with some plasticizer as carrier, can, if desired, pump in-line the pigment and, if desired, also a fungicide, and be mixed in using a static mixer.

Further details were carried out as described in Example 1, with the difference that in this example the mixing tub remained always closed, i.e. the lid remained on the mixing tub and no manhole or opening to the ambient air was opened.

After the mixing bowl was emptied, the next production batch was immediately started by directing new quantities of ingredients to the mixing bowl.

Now that this invention has been fully described, those skilled in the art will realize that the invention can be implemented with a wide range of parameters within what is claimed, without, therefore, departing from the scope of the invention as defined by the claims.

Claims (61)

CONCLUSIONS A method of manufacturing a composition capable of curing under the influence of moisture, wherein the reactive end groups of a reactive polymer are reacted with a crosslinker to form the prepolymer, the product being filled in a plastic tube as a final package and the tube is sealed after filling by placing a "kolb" or plunger in the open end of the tube, characterized in that the tube is provided on the inside, at least at the place where the tube must come into contact with the tube of a layer of lubricant, and in that in the reaction to form the prepolymer, the crosslinker is added in a stoichiometric excess with respect to the amount of reactive end groups present on the reactive polymer. The method of claim 1 wherein the layer of lubricant has a thickness of no more than 0.20 mm and optionally a thickness of at least 0.01 mm. The method according to claim 1 or 2, wherein the lubricant contains at most 100 ppm of water. The method of any one of the preceding claims wherein the lubricant has a vapor pressure at room temperature of at most 1.0 hPa. The method of any one of the preceding claims wherein the lubricant is one of the plasticizers selected from the formulation of the composition that is filled into the sheath. The method of any one of the preceding claims wherein the lubricant is a silicone oil. The method of any one of the preceding claims wherein a molar ratio of crosslinker to the number of molecules of reactive polymer present of at least 3.0: 1.0 molar is used. The method according to any one of the preceding claims wherein a molar ratio of crosslinker to the number of molecules of reactive polymer present of at most 60: 1 molar is used. The method according to any one of the preceding claims, wherein the product comprises one or more fillers, the filler being formed either by milling or by precipitation or precipitation, characterized in that the milled filler contains at most 2000 ppm by weight of water, and the precipitated filler contains no more than 8000 ppm weight of water. The method of the preceding claim wherein the filler is a ground filler comprising at most 1500 ppm by weight of water. The method of claim 9 or 10 wherein the milled filler comprises at least 100 ppm by weight of water. The method of claim 9 wherein the filler is a precipitated filler containing at most 7500 ppm by weight of water. The method of the preceding claim wherein the precipitated filler comprises at least 1000 ppm of water. The method according to any of claims 9-13 wherein the filler is selected from the list consisting of calcium carbonate, preferably ground calcium carbonate (GCC), dolomite, with which a mixture of mainly calcium and magnesium carbonate refers to, and precipitated (precipitated) calcium carbonate ("precipitated calcium carbonate", PCC). The method of any one of claims 9-14 wherein the filler is coated. The method according to any of claims 9-15 wherein the filler is pneumatically transported to the mixing plant where the filler is mixed in at least one of the liquid ingredients required to obtain the end product, wherein preferably the carrier for the pneumatic transport is a gas with a dew point of 0 ° C or less. The method according to the preceding claim, wherein nitrogen or air is used as carrier for the pneumatic transport. The method according to the preceding claim wherein the carrier is ambient air that is pressurized and dried to the desired dew point before the air is used for pneumatic transport. The method according to the preceding claim wherein the air is dried by cooling it to a temperature of at most the desired dew point, whereby the excess moisture in the air condenses and can be physically separated, and whereby a dried air remains with a moisture content of at most the desired dew point. The method of any one of the preceding claims wherein at least a portion of the ingredients are introduced into a mixing tub and mixed, wherein they also react with each other in the mixing tub as necessary, and wherein at least during a portion of the method the mixing tub with contents being placed under vacuum, wherein the mixing tub is provided with an outlet mouth, and wherein the outlet mouth is closed by means of a plastic foil during filling, mixing and / or reacting. The method according to the preceding claim wherein the plastic film closing the outlet mouth consists of a thermoplastic and the thermoplastic film is thermally welded, as a membrane, on the outlet mouth or preferably on an additional plastic intermediate piece which is attached to the outlet mouth, and preferably this intermediate piece is screwed onto the outlet mouth. The method of any one of claims 20-21 wherein the mixing bowl lid comprises an inspection window and the mixing tube includes an outlet mouth that was temporarily sealed with a lid, and the method includes visual inspection by the inspection window whether there are air bubbles from the liquid and those air bubbles come from a leaking lid on the outlet mouth, characterized in that an elastic sleeve is pulled over the lid on the outlet mouth and its connection to the outlet mouth. The method according to any of claims 20-22 wherein, to remove the mixed and reacted end product from the mixing tub, the plastic film closing the outlet mouth is punctured, preferably through a suitable drain valve to which the outlet mouth is connected and with which the mixing tub is connected to the filling installation to fill and package the contents of the mixing bowl. The method of any one of the preceding claims wherein the reactive polymer is reacted with a cross-linker in a mixing vessel and wherein the method, after homogeneously stirring the liquid in the mixing vessel, containing the reactive polymer, and also after venting the closed mixing vessel by placing it under negative pressure, adding includes in the mixing vessel of the crosslinker to react with the reactive end groups of the reactive polymer and thereby form the prepolymer and possibly additionally adding an extender to the contents of the mixing vessel , characterized in that before and preferably also during the addition of the crosslinker, the mixing tub is placed under an overpressure, preferably at an overpressure of at least 0.1 barg. The method according to the preceding claim wherein at least one of the ingredients of the composition, for example a filler, is supplied by pneumatic transport, characterized in that the excess pressure is achieved by adding at least one of the gases that are used for that pneumatic transport. The method according to any of the preceding claims, wherein during the reaction of the cross-linker with the reactive polymer, an underpressure is set, preferably of at most 0.50 bar absolute (bara), and optionally of at least 0.001 bara or 1 mbar absolute. The method according to any one of the preceding claims, wherein the closed mixing tub is placed at least temporarily under an underpressure, said underpressure being broken by admitting a gas into the mixing tub, preferably dried air, more preferably an air that has a dew point has a maximum of -40 ° C, preferably a maximum of -45 ° C, more preferably a dew point of a maximum of -50 ° C. The method according to any of the preceding claims, wherein the cross-linker is added to the mixing vessel, characterized in that the cross-linker is dispersed in the contents of the mixing vessel and that a slight overpressure is maintained in the mixing vessel in the range of 0.05- 0.30 barg. The method of any one of the preceding claims wherein the stirring speed of the stirrer in the mixing vessel during the reaction of the crosslinker with the reactive polymer is limited to at most 300 rotations per minute. The method according to any of the preceding claims, wherein, after the cross-linking agent has been mixed into the liquid in the mixing vessel, and preferably only after the dispersing of the cross-linking agent, the mixing vessel is placed under an underpressure, the underpressure preferably being at most 0.5 bar absolute (bara). The method according to any one of the preceding claims which uses a mixing tub for the production of the prepolymer by the reaction of a reactive polymer with a crosslinker, wherein after the introduction of at least one liquid reagent for the reaction or another liquid ingredient of the formulation, the contents of the mixing tub are stirred and the closed mixing tub is placed under an underpressure, the underpressure being at most 0.50 bar absolute (bara). The method according to the preceding claim wherein the mixing tub is closed and an underpressure is achieved of at most 0.40 bara within 60 seconds after the mixing tub is closed. The method according to the preceding claim wherein an underpressure is achieved of at most 0.20 bara within a period of 120 seconds after the mixing bowl is closed. The method according to any of claims 31-33 wherein the mixing tub is closed by joining the mixing tub and the lid, characterized in that a sealing ring is placed between mixing tub and lid, and that the material of the sealing ring has a Shore A hardness according to ASTM D2240 has at least 30 and at most 80. The method of the preceding claim wherein the seal ring is formed from a compound that is a blend of polypropylene with ethylene / propylene / diene monomeric plastic. 36. The method according to any of the preceding claims, wherein the process proceeds in a batch and the production of the prepolymer takes place in a mixing vessel, characterized in that, after obtaining the prepolymer in the mixing vessel, the lid of the mixing vessel is lifted and the stirrer and / or scraper is retrieved from the liquid, the mixing tub is closed by means of two sheets of plastic film, the first sheet being applied to the product as well as possible and against the upright wall of the opened mixing tub, and then a second sheet is stretched over the top edge of the mixing bowl. The method according to the preceding claim wherein the collected stirrer and / or scraper is scraped off, preferably manually with a suitable knife, and the scraped product is dropped into the mixing tub before the mixing tub is sealed with the plastic films. The method of any one of claims 36-37 wherein an amount of desiccant is provided between the two plastic films. The method according to any of claims 36-38, wherein the ambient air between the two plastic films is at least partially replaced by a dry gas. The process according to any of claims 1-35 wherein the process proceeds in batch and uses a mixing vessel for the production of the prepolymer, characterized in that the reactive polymer and the cross-linker, as well as the additional ingredients required for the production step into the mixing tub, into the closed mixing tub and react without opening the mixing tub, and mixing occurs without opening the mixing tub, and also the product is removed from the mixing tub without opening the mixing tub. The method according to the preceding claim wherein the mixing tub is closed with a lid and the lid of the mixing tub is provided with a height-adjustable stirring system such that, without having to open the mixing tub by lifting the lid, the height adjustment of the stirrer relative to the liquid level in the mixing bowl can be adjusted. The method according to any of claims 40-41 wherein the mixing tub is kept under vacuum during the addition of the reactive polymer and the cross-linker, preferably also during the addition of the plasticizer and / or the extender, if applicable. The method according to any of claims 40-42 wherein a thickener is added to the mixing tub, and wherein the mixing tub is kept under approximately atmospheric pressure during the addition of the thickening agent, and, if there is an underpressure in the mixing tub, this underpressure becomes broken before adding the thickener. The method according to the preceding claim wherein a thickener is introduced pneumatically into the mixing tub, preferably into a stream of air, preferably a stream of dried air. The method of any one of claims 40-44 wherein the mixing tub is kept under a vacuum during pumping out of the product from the mixing tub. The method according to any of claims 40-45, wherein the stirrer arms in the mixing tub are provided with scrapers that extend up to a distance of at most 5 mm away from the side walls of the mixing tub. The method of any one of claims 40 to 46 wherein the bottom of the stirrer has substantially the same shape as the bottom of the mixing tub, preferably with a tolerance of at most 5 mm. The method according to the preceding claim, wherein the underside of the stirrer is additionally provided with a rubber strip over substantially the full width. The method according to any of claims 40-48 wherein at least one upwardly projecting protrusion is provided on each of the two arms of the stirrer, which protrudes into a point with an angle of at most 45 degrees, which corresponds to at most one eighth circle. The method of the preceding claim wherein the upwardly directed pointed protrusions on the arms of the stirrer are provided on the outer 60% of the stirrer arm. The method according to any of claims 40-50, wherein at least one upwardly directed blade is provided on each of the stirrer's arms, which blade forms an angle with the longitudinal axis of the stirrer arm that is less than 90 degrees or a quarter circle. The method according to any of claims 40-51 wherein several of the different ingredients are added to the mixing tub simultaneously, and this while the stirrer has already been operated. The method of any one of claims 40 to 52 wherein the product is pumped from the mixing tub to a buffer tank before the product is filled into its final package. The method according to the preceding claim wherein the product is pumped out of the buffer tank and mixed into the pigment and / or fungicide product downstream of the buffer tank before the product is filled into its final package. The method according to any of claims 53-54 wherein the product in the buffer tank is a transparent product and the product is pumped out of the buffer tank and the desired amount of filler is mixed into the product downstream of the buffer tank before the product is filled into his final packaging. The method of any one of claims 40 to 55 wherein at least one of, and preferably all of, the liquid ingredients of the production procedure are stored in separate feed tanks in which the atmosphere above the liquid consists of dried air prior to their transfer to the mixing vessel. The method of any one of claims 40 to 56 wherein the reactive polymer and the crosslinker are premixed on the way to the mixing tub and react to an at least partially encapsulated prepolymer. The method of the preceding claim wherein the at least partially grafted prepolymer is fed to the mixing tub from below. The method of any one of claims 57-58 wherein thickener is added to a space in which the already at least partially, and preferably the fairly fully, grafted prepolymer is gradually fed by pressing the prepolymer through a narrow elongated opening or slot such that a liquid curtain is formed. The method of the preceding claim wherein the thickener additive mixture passes through an intermediate mixer. The method according to any of claims 40-60, wherein an intermediate product without filler is produced in the mixing tub.