Technical Field

The invention relates to a low density semi-rigid polyurethane foam for use in different fields such as indoor insulation applications, packaging and automotive as a sound absorption and heat insulation material, especially a sound insulation material, and an anti-vibration and/or anti-impact material, and to a method for the production thereof.

In particular, the invention relates to a low density semi-rigid polyurethane foam applicable in spray form, which is prepared by using catalysts with reduced emission and fully blown with water, without using any external emulsifier as a compatibilizer, and to a production method thereof.

State of the Art

Polyurethane foams (PUF) are two-component systems in which an isocyanate (component A) and a polyol (component B) expand by means of a blowing agent during the polymerization reaction and form a foam, according to the traditional production technique. In low-density PUF systems, component B is a complex system in which many raw materials with different activity levels are used as an input, and the performance characteristics of the polyurethane foam may be improved with appropriate additions to the component B. The component B essentially consists of a parent polyol and water as a blowing agent, silicone surfactants (surfactants), emulsifiers (compatibilizers), catalysts, flame retardants, cell openers and other suitable additives.

In low-density semi-rigid polyurethane foams (SRPUR), the open cell content is more than 80%, and the apparent density of the foam is usually in the range of 5-20 kg/m ³ . Production of a low-density polyurethane foam, such as 6-10 kg/m ³ , requires the use of a high amount of water (>15% by weight), which is preferred as a chemical blowing agent in the formula of component B. The low-density SRPUR systems using only water as a blowing agent have an Ozone Depletion Potential (ODP) of 0 and a Global

Warming Potential (GWP) of 1 , and their environmental impact is much lower than that of other physical blowing agents. However, the high water content in the component B causes undesirable phase separations by negatively affecting the phase stability of the component during a long-term storage. It is difficult to detect this phase separation in the process from formula preparation of a formulator to the storage of the product, from the transportation of the product to the use of the product by the practitioner. This requires the practitioner to re-mix the product under appropriate conditions before each use. However, if the material cannot be mixed effectively in the application area, this phase separation causes undesirable changes in the reaction rate, the cell structure of the foam and the final product performance characteristics such as physical, thermal and mechanical strength.

In prior art, emulsifiers were added to the component B to solve the phase separation problem. These emulsifiers are generally alkylphenol ethoxylates and are mostly used as nonylphenol ethoxylates (NPE). The patent application no. W00046266A1 discloses such emulsifiers and general methods for the preparation of polyurethanes using them.

Recent studies have shown that NPEs have weak estrogen-like properties or may be endocrine disruptors. Therefore, nonylphenols (NP) and NPEs are under review by the Environmental Protection Agency (EPA) according to the new Chemical Action Plan (CAP) program (Nonylphenol (NP) and Nonylphenol Ethoxylates (NPEs) Action Plan, 2010, EPA). To implement this action plan, EPA's Design for the Environment (DfE) Program has released the 'Alternatives Assessment for Nonylphenol Ethoxylates'. This report describes the criteria that define safer emulsifiers as alternatives to NPE and lists examples of the emulsifiers that meet the criteria (DfE Alternatives Assessment for Nonylphenol Ethoxylates, 2012, EPA). NPE and NP, the decomposition product thereof, and other decomposition components are toxic substances harmful to living and environmental health that can seriously endanger aquatic life even at low concentrations. Therefore, there has been a tendency towards harmless alternatives to NPEs in the future studies. The patent application no. WO2012021675A2 discloses water-blown polyurethane foam formulations containing mixtures of alkylethoxylate alcohols or alkyl alcohol ethoxylate (AAE) with an HLB value of 10 to 15 as an emulsifier (compatibilizer) instead of NPEs that have been determined to be harmful. The effects of the widely used standard emulsifier NPE-9 and the compatibilizers described as Emulsifier-A (AAE with an HLB of 13.1 ) and Emulsifier-B (AAE, >50% mass of which is derived from a renewable carbon source) on the phase separation of the polyol mixture (component B) were investigated comparatively. However, formulations containing alkyl alcohol ethoxylate (AAE) have disadvantages such as continuation of the potential of a phase separation during long-term storage despite the high emulsifier content and increase in the production cost, as well as the negative effects they may cause on the environment.

With reference to referring to the technique of the patent application WO2012021675A2, the patent application no. US20180086873A1 has stated that NPE-free compatibilizers are used in some techniques, but that these emulsions will cause a phase separation in component B during long term storage. Based on these reasons, it has been explained that the alkoxylated natural oils can be used as emulsifiers in order to prevent the formation of a phase separation in the component B with high water ratios and that they can be used instead of traditional polyethers to produce a water-blown low density spray foam. Different from this technique, a formulation design of the component B is disclosed in the present invention, which remains stable throughout the shelf life for use in the production of low density SRPUR in which the correctly selected commercial polyether polyols and appropriate additives are used without the use of any external emulsifier. Again, unlike the patent application no. US20180086873A1 , the catalysts with no emission and/or reduced emission are used in the formulation of the present invention, instead of tertiary amine catalysts (for example, bis-(2-dimethylaminoethyl) ether), which are known to affect the health of living things with their environmental effects.

In the production of low-density polyurethane foams such as 6-10 kg/m ³ , suitable catalysts with high reactivity are needed so that a high amount of water and isocyanate can react. In prior art, amine catalysts are generally used for this. Bis- (dimethylaminoethyl)-ether (BDMAEE) is defined as the most reactive blowing catalyst with the molecular structure thereof. However, these and similar amine catalysts are catalysts with high emissions due to their high vapor pressure and strong amine odor. During formula preparation and spraying, amine exposure occurs when people are exposed to this vapor during the use of the foam, and this causes temporary blue-gray or blurred vision (glaucopsia). The patent document no. EP2736937B1 discloses the preparation of low density (6-16 kg/m ³ ) polyurethane foams, which are fully water- blown, using catalyst components with low amine emission, by considering these disadvantages. The related document discloses a catalyst package containing at least one emission-free catalyst and tetraalkyl guanidine, a method of application and a formulation containing this catalyst package. According to this aspect, the patent document no. EP2736937B1 uses NPE-based compatibilizers, which are found to be harmful to the environment and living things although it defines an approach similar to the current patent study.

The patent application no. US4087389A discloses the production of low-density (8 kg/m ³ ) SRPURs prepared by using a high amount of water and organic blowing agents for use in the packaging of fragile and shock-sensitive objects. The application uses a high amount of organic (physical) blowing agents along with water. Physical blowing agents are generally low-boiling liquid hydrocarbon materials, and they pass into a gas state with the exotherm heat generated during the polyol-isocyanate reaction and are trapped in the foam cells by causing the foam to blow. The organic blowing agent (trichlorofluoromethane- Feron 11) used in the invention harms public health and the environment by destroying ozone in the atmosphere.

Considering the reasons explained in the state of the art, there is a need for new formulations with simple content and reduced environmental impact, which do not contain an external compatibilizer for the production of low density SRPUR, have a reduced amine catalyst emission, do not form phase separation under storage conditions, provide the design of products with long shelf life (>6 months), and new techniques or methods which form these formulations.

Consequently all the above-mentioned disadvantages and drawbacks have made it necessary to make an innovation in the relevant technical field. Object of the Invention

The present invention relates to a low density semi-rigid polyurethane foam (SRPUR) applicable in spray form, which meets the above-mentioned requirements, eliminates all disadvantages and provides some additional advantages.

The object of the invention is to provide to a low density semi-rigid polyurethane foam (SRPUR) applicable in spray form which is used for different fields such as indoor insulation applications, packaging and automotive as a sound and heat insulation material, especially a sound insulation material, and a vibration and/or impact absorbing material, and which is prepared by using catalysts with reduced emissions and by being blown fully with water, without the use of any emulsifier.

The object of the invention is to provide a low-density (especially 6-10 kg/m ³ ) semi-rigid polyurethane foam (SRPUR) formula, which contains amine catalysts with reduced emission in an amount and content so as to provide a low density value without using any emulsifiers to provide phase stability despite high water content.

The object of the invention is to present a fully water blown low density semi rigid polyurethane foam (SRPUR) which does not contain any external compatibilizer, including harmful emulsifiers such as NPEs or NPE-free emulsifiers containing alkyl alcohol ethoxylates (AAE), the use of which is acceptable by EPA, wherein the low density semi rigid polyurethane maintains its phase stability throughout shelf life.

Another object of the invention is to provide a low density semi-rigid polyurethane foam (SRPUR) formula which does not contain catalysts that cause harmful emissions to the practitioner and the end user.

The object of the invention is to provide a low density semi-rigid polyurethane foam (SRPUR) formula which can remain stable for a long time (>6 months) without phase separation, making it easier for the practitioner to use it without the need for any mixing process before spray production. The object of the invention is to prepare a low density semi-rigid polyurethane foam (SRPUR) systems with an Ozone Depletion Potential (ODP) of 0 and a Global Warming Potential (GWP) of 1 , by using only water as a blowing agent, thus revealing the design of products with reduced environmental impacts.

One object of the invention is to produce low-density semi-rigid polyurethane foam (SRPUR) materials that are less harmful to the environment and living things with a simple formula.

Another object of the invention is to produce low density semi-rigid polyurethane foam (SRPUR) materials, which provide sound absorption and heat insulation efficiency, with a simple formula design so as to provide a low-cost production.

To achieve the above-mentioned objects, the invention is a low density semi-rigid polyurethane foam (SRPUR) for use in different fields such as indoor insulation applications, packaging and automotive as a sound absorption and heat insulation material, especially a sound insulation material, and a vibration and/or impact absorbing material, characterized in that the formulation comprises a component A consisting of at least one isocyanate and a component B which reacts with the component A and contains at least one parent polyol (polyol 1), a catalyst with no and/or reduced emission, more than 15% by weight of water as a blowing agent, at least one silicone surfactant and at least one flame retardant.

To achieve the above-mentioned objects, the invention is a method of producing a low density semi-rigid polyurethane foam for use in different fields such as indoor insulation applications, packaging and automotive as a sound absorption and heat insulation material, especially a sound insulation material, and a vibration and/or impact absorbing material, characterized in that it comprises the following process steps: a) adding at least one polyol 1 , polyol 2, a flame retardant, more than 15% of water as a blowing agent, at least one catalyst with no emission and/or reduced emission and at least one silicone surfactant in a container, and mixing at a speed of 500-2000 rpm, thereby obtaining a premix b) mixing the premix at 10-45 °C, at a mixing speed of 1000-2000 rpm for 0.5-5 minutes, c) preparing the component B by adding the blowing agent to the mixture at a mixing speed of 500-2000 rpm and mixing, and after the addition, mixing for 0.5-60 minutes at 1000-2000 rpm, d) impinging the component A and the obtained component B at a ratio of 0.8:1.0 - 2.0:1.0 by weight, preferably 1.05:1.0 - 1.4:1.0 in a mixing head of a high pressure machine and spraying onto the suitable surfaces to form low density SRPUR using a foam spray gun.

The structural and characteristic features and all advantages of the invention will be understood more clearly with the detailed description below and thus, the evaluation should be made by taking these figures and the detailed description into consideration.

Detailed Description of the Invention

In this detailed description, the low density semi-rigid polyurethane foam (SRPUR) applicable in spray form is described only for a better understanding of the subject and in a non-limiting sense.

The invention relates to a low density semi-rigid polyurethane foam for use in different fields such as indoor insulation applications, packaging and automotive as a sound absorption and heat insulation material, especially a sound insulation material, and an anti-vibration and/or anti-impact material, and to a method for the production thereof.

In particular, the invention relates to a low density semi-rigid polyurethane foam (SRPUR) applicable in spray form, which is prepared by using catalysts with reduced emission and fully blown with water, without using any external emulsifier as a compatibilizer, and to a production method thereof.

The invention reveals a formula which ensures the component B with more than 15% of water content and to which an emulsifier is not added to remain stable throughout the shelf life without a phase separation. The invention includes the content of component B, in which harmful nonylphenol ethoxylate (NPE) components and the alternatives thereof, alkyl alcohol ethoxylates (AAE) are completely removed and the catalysts with reduced emission are used instead of harmful amine catalysts and water is used as the blowing agent.

The component B of the formulation according to the invention may contain polyols, water as a blowing agent, flame retardants, amine catalysts, silicone surfactants as well as metal catalysts, cell openers, crosslinkers, chain extenders, pigments, antioxidants, fillers, reinforcing materials and also other additives. Besides, it is possible to add some additives to the component A (isocyanate) side.

The low-density semi-rigid polyurethane foams (SRPUR) are a synthesis product of the component B consisting of the main polyol having hydroxyl (OH) end groups and the additives, and isocyanate having NCO end groups, also known as the component A, and is obtained by an exothermic polymerization reaction. Parameters such as the appropriate polyol/isocyanate ratio, temperature of the components, and mixing speed and time are important process parameters that affect the properties of polyurethane foams.

The open/closed states of the cells in SRPURs are the most important structural parameter which affects the sound insulation capability. The regulation of the open/closed cell ratio is provided by mechanisms such as controlling the viscosity increase and phase separation during foam formation, and controlling the distribution of flexible and rigid segments in the foam structure. The control of these mechanisms is possible by the reaction of the component B, which will be prepared with the right polyol package and auxiliary raw materials such as silicones, catalysts, cell openers, etc. compatible with that package, with the appropriate component A, under the right process conditions.

Depending on the characteristics of the polyols selected within the scope of the invention, a high amount of water is retained in the polyol (component B). The selected polyether polyols are used here as a compatibilizer which both forms the foam structure and retains large amounts of water in the component B. It is possible to provide the phase stability of the component B by selecting the other additives (a surfactant, a catalyst, a flame retardant, etc.) included in the formula so as to support the polyol-water compatibility. Accordingly, a low density semi-rigid polyurethane foam (SRPUR) formula and a production method thereof are described, wherein the low density semi-rigid polyurethane foam allows the component B having a water content of more than 15% to remain stable throughout the shelf life thereof with polyether polyols selected in the present invention, catalysts with reduced emission and nonhydrolyzed silicone copolymer surfactants, without the need for an external emulsifier. With the amount and compatibility of all these inputs in the formulation, there is no phase separation in the component B which is kept at room conditions for longer than 6 months, and SRPUR obtained from the reaction of the component B with the component A is in the form of a small, regular and low density sprayable foam with more than 90% open cell structure.

Polyol means a compound with an average hydroxyl (OH) functionality of two or more (i.e., the compound contains, on average, greater than or equal to two OH groups per molecule of the compound). A particular polyol has some important properties which determine the performance characteristics it will show in the polyurethane structure. These are the hydroxyl number or hydroxyl value (OH value), OH equivalent weight and molecular weight of the polyol and the functionality of the polyol.

A polyol has an average molecular weight (by weight, or in number) of between 100 and 10000 Da and an average functionality of between 2 and 8. Polyols with a molecular weight of 1000 to 6000 Da and a functionality of 2 to 3 are used in flexible polyurethane foams and elastomers. The more rigid polymer chains with more crosslinking are obtained with polyols with molecular weight below 1000 Da and high functionality. These polyols are used in the production of rigid polyurethane foams with high chemical and thermal resistance.

The polyol may be a polyether (polyalkylene ether) polyol or a polyester polyol. Polyester polyols are produced by a polycondensation reaction of the polyfunctional carboxylic acids and polyhydroxy compounds. Polyfunctional carboxylic acids that can be used are adipic acid, phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid or maleic acid. Multifunctional hydroxyl compounds that can be used include: ethylene glycol, diethylene glycol, triethylene glycol, 1 ,2 propylene glycol, dipropylene glycol, 1 ,3- butanediol, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,12-dodecanediol, neopentyl glycol, trimethylolpropane, trietilolpropane, or glycerol (glycerin).

Polyether polyols include poly(alkyleneoxide) polymers such as poly(ethyleneoxide) and poly(propyleneoxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols. Polyether polyols are traditionally prepared from an addition reaction of epoxies or cyclic ethers (e.g. ethylene oxide (EO), propylene oxide (PO), etc.) with the compounds with active hydrogen atom acting as an initiator in the presence of a suitable catalyst (e.g. KOH, DCM, etc.).

The amount of each oxide and the order of addition affect the compatibility, water solubility and reactivity of the polyol. Polyols containing only PO are largely terminated by the secondary hydroxyl groups and are less reactive than the EO-coated polyols with primary hydroxyl groups. To obtain polyols with more reactive primary hydroxyl groups, the polymerization is initiated with PO, and EO is added during the final step. This polyol is called EO-capped/terminated polyether polyol. The EO-capped polymer backbone increases the water solubility of the polyol.

The initiator alcohols used in the production of polyether polyols that can be used within the scope of the invention are, but not limited thereto, ethylene glycol, propylene glycol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol, diglycerol, trimethylol propane, triethanolamine, cyclohexane diol, pentaerythritol, and sugars such as sorbitol or saccharose (sucrose) or similar low molecular weight polyols.

The initiator used to produce the polyol may affect the reactivity as well as the functionality of the polyol. Amines may also be used instead of alcohols to increase polyol reactivity. Amines which may be used may be ethylene diamine, toluene diamine, 4,4'-diphenylmethane diamine and diethylenetriamine. The resulting polyols exhibit a higher alkalinity than polyols containing an alcohol as an initiator and are therefore more reactive with isocyanates. Examples of polyols suitable for use in the invention may include at least one member selected from the group consisting of polyether and polyester polyols described above. In the present invention, at least one main polyol, a high molecular weight polyether polyol, is used to produce the low density semi-rigid polyurethane foam (SRPUR). In another aspect of the present invention, a mixture of auxiliary polyols of different functionality and/or different molecular weight and/or different chemical composition may be used together with the parent polyol. The total amount of polyol used in the present invention is typically about 5-75%, peferably 20-60%, by weight of the component B formulation.

Parent polyol (Polyol 1)

The low-density semi-rigid polyurethane foams (SRPUR) have a partially flexible, opencell structure. The properties of SRPUR depend on the additives such as catalysts and surfactants, and polyisocyanates, especially on the structure of polyether polyols used in the formula.

The functionality of the polyether polyols, the chain length, the type of epoxies used in their production (such as PO and EO) and the ratio of epoxies have a great influence on the processability of the polyether polyols and the properties of the polyurethane foams produced from these polyether polyols.

Polyether polyols suitable for the production of flexible polyurethane foams generally have a hydroxyl (OH) functionality of between 2 and 4. These polyether polyols are obtained by adding either PO alone or a PO/EO mixture with a PO content of at least 70% by weight to a initiator compound with a suitable OH functionality. However, polyether polyols with a high EO content (i.e., >70% EO content by weight) are also used for the production and cell opening of a series of polyurethane foams, such as soft, ultrasoft foams and viscoelastic foams.

Polyether polyols containing high amounts of EO units typically have a 3-block structure. In a "3-block structure", the initiator compound (e.g., glycerol) is first extended with PO only, thus forming a pure PO block. Then, this reacts with a mixture of EO and PO to form a mixed block with a random distribution of EO and PO units, and then reacts only with EO in the third step to obtain a pure EO block at the chain end. The result is a 3-functional, EO-terminated polyoxyethylene/polyoxypropylene copolymer. These polyether polyols having a 3-block structure generally have EO units of >70% by weight.

When polyether polyols have EO ends, the resulting OH groups are primary hydroxyls. PO ends mostly provide secondary OH groups. As a result of the increased steric hindrance, the secondary OH groups react more slowly than the primary OH groups. EO-capped polyether polyols, the terminal end groups of which have high primary OH end groups, on the other hand, provide relatively higher reactivity with isocyanates. However, EO is more hydrophilic and therefore polyether polyols containing EO are more hydrophilic than those produced with polyether polyols made with PO alone. The hydrophilic feature of polyether polyols with EO content provides them with emulsifying (compatibilizer) characteristics.

In the prior art, the conventional polyether polyols used in the production of low density SRPUR are generally 3-functional polyether polyols with a PO content of 20-60 mg KOH/g OH, or with a low EO content. These polyether triols, preferably used together with an auxiliary cell opener, have generally a glycerine initiator and polymerized with PO and then terminated with about 20% of EO. The conventional polyether polyols are polyether triols with 10-15% of EO end groups, specifically having an OH number of 34-37 mg KOH/g and a molecular weight of 4500-4800. In the formulation of the component B in which such polyols are used, the phase separation occurs in the component B by the accumulation of water over the surface in general, by the effect of lipophilic additives used together with a high (for example, more than 10% by weight) amount of water.

In the present invention, it is intended to produce a component B which may remain stable without a phase separation throughout the shelf life by means of the formulation design of the component B which has better hydrophilic properties, that is, which is arranged with polyether polyols having a high EO content, and a low density SRPUR foam such as 6-10 kg/m ³ by using that component B. The parent polyol (Polyol 1) used in the present invention forms the SRPUR structure with a high % of open cell structure that increases the sound insulation capability, while acting as an emulsifier depending on the EO content so as to ensure the high water content and lipophilic additives to remain in the component B without a phase separation. Accordingly, the Polyol 1 used in the present invention is a polyether polyol having more than 20% EO-terminated polymer chain configuration. Polyol 1 is preferred over the EO-terminal ended polyoxyethylene/polyoxypropylene polyether polyols ranging from about 25-40% by weight. In another aspect of the present invention, Polyol 1 contains EO which is dispersed/located within the polyether polyol backbone, and/or which is present in the terminal end groups, and the total EO content, including the internal EO content and the EO content in the end groups, is more than 30%, preferably in the range of 35- 80%, by weight, of the polyether polyol. In another aspect of the present invention, Polyol 1 may be an initiator in the polymer chain structure and a polyether polyol containing only EO with a high reaction activity.

In the present invention, Polyol 1 may have ethylene glycol, propylene glycol, 1 ,3- butane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol initiators, etc. to form a polyether diol. In the present invention, Polyol 1 may have glycerine, trimethyl propane (TMP), triethanolamine initiators, etc. to form a polyether triol. In another aspect of the present invention, Polyol 1 may be a tetrol with a sorbitol initiator. Without being limited to the foregoing, Polyol 1 is obtained from the initiators with different functionality, or the PO and EO reaction of the initiators consisting of combinations thereof.

In the preferred embodiment of the invention, polyoxypropylene/polyoxyethylene polyol with an average molecular weight of 4000, an OH number of 26-30 mg KOH/g and an EO end of more than about 25% by weight is used as Polyol 1. This polyol 1 is polyether diol with a high EO content, initiating from propylene glycol, with a terminal group copolymerized with propylene oxide and ethylene oxide being a high primary hydroxyl. Another Polyol 1 used in the preferred embodiment of the invention is a high EO content polyether triol with an average molecular weight of 4500 and an OH number of 33-37 mg KOH/g, with a glycerine initiator, wherein polyether triol contains a total of about 80% EO by weight within, and at the end, of the polymer backbone. Polyol 1 s preferred in the invention are commercial polyether polyols and may be used instead of any suitable polyether polyols with these properties obtained from different manufacturers, or polyether polyols with similar properties may be synthesized and used. The amount of Polyol 1 used in the present invention is typically about 5-60%, peferably 15-50%, by weight of the component B formulation.

Auxiliary Polyol (Polyol 2)

In the present invention, a single polyol of different functionality and/or molecular weight and/or chemical composition or a mixture thereof may be used as the auxiliary polyol (Polyol 2).

Polyether polyols with high OH number (and high functionality) and low molecular weight, known as rigid polyurethane foam polyols, may be used in the present invention. While not being limiting, the polyether polyols with a sucrose initiator having 8 functionalities, a sorbitol initiator having 6 functionalities, a Mannich initiator having 4 functionalities, a toluendiamine initiator having 4 functionalities or a glycerine initiator having 3 functionalities may be preferred as auxiliary polyols.

In another aspect of the present invention, high molecular weight (1000-10000 Da by weight or in number) polyether polyols with 2, or greater than 2 and less than 4 functionalities , known as flexible polyurethane foam polyols, may be used as Polyol 2. These polyols are, but not limited to, polyether polyols obtained from the reaction of ethylene oxide (EO) and/or propylene oxide (PO) with alcohol initiators as previously described, and are preferably polyether polyols with a functionality of ranging between 2 and 3 and an OH value of ranging between 18 and 400 mg KOH/g.

A special class of polyether polyols is poly(tetramethylene ether) glycol made by polymerization of tetrahydrofuran and may be used in the present invention as Polyol 2. Phosphor-containing polyols, which impart flame retardant properties to the polyurethane foam, may also be preferred as polyol 2.

In yet another aspect of the present invention, polyester polyols can be used as Polyol 2, including those produced when a dicarboxylic acid reacts with an excess of diol. Non-limiting examples include adipic, succinic, glutaric, pimelic, suberic, azelaic acid or phthalic acid, or phthalic anhydride which reacts with ethylene glycol or 1 ,4-butanediol (1 ,4-BDO). In the present invention, sustainable polyester polyols produced by transesterification (glycolysis) of the recycled polyethylene terephthalate) or dimethyl terephthalate in the presence of glycols such as diethylene glycol may be used as Polyol 2. Examples of auxiliary polyols that can be used in the present invention are caprolactone, which is produced by reacting a lactone with an excess of diol, for example is reacted with propylene glycol.

In the present invention, biopolyols derived from other vegetable oils, commonly castor oil, may be used as Polyol 2. Although not being limited, polyols prepared from the renewable resources such as vegetable oils, vegetable oil derivatives, sorbitol and cellulose may be preferred. Other useful biopolyols that can be used include those produced from natural oils such as castor oil, soybean, palm or canola, and sugars, sucrose or a biomass.

In the preferred embodiment of the invention, a polyether polyol with sucrose initiator, which have an average OH value of 450 mg KOH/g and an OH functionality of more than 4, is used as polyol 2. A commercial polyether polyol is preferred in the invention, and any suitable polyether polyol with these properties from different polyether polyol manufacturers may be used.

Another polyol used as Polyol 2 in the preferred embodiment of the invention is a castor oil based biopolyol with an OH value of 210 mg KOH/g and a functionality of 2- 2.5. A commercial polyether polyol is preferred in the invention, and any suitable biopolyol with these properties supplied from different producing companies may be used.

In the present invention, including those described above, polyols with different chemical components and different functionality may be used as auxiliary polyols to impart new properties to the low density semi-rigid polyurethane foam. The amount of Polyol 2 used in the present invention is typically about 0-40%, preferably 8-25%, by weight of the component B formulation.

Blowing agent These are auxiliary substances that expand the foam structure by turning from the liquid phase to the gas phase by the effect of the heat released during the reaction of polyol and isocyanate. During the polyurethane production, the most suitable way to blow the polymer is the in situ production of carbon dioxide by reaction of isocyanates with water. The primary blowing agent according to the present invention is water, and the total blowing agent used in the formula may be water, or it is possible to add auxiliary blowing agents together with water to the formulation. However, these auxiliary blowing agents are relatively expensive compared to the existing materials such as carbon dioxide.

The auxiliary blowing agents may include hydrocarbons such as n-pentane, cyclopentane and isopentane, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrochlorofluoroolefins (HCFOs), fluoroolefins (FO), methylenechloride, acetone, and combinations thereof. Examples of hydrofluorocarbons (HFCs) are HFC-245fa, HFC-134a, and HFC-365, and examples of hydrochlorofluorocarbons (HCFCs) are HCFC-141 b, HCFC-22, and HCFC-123.

The use of chlorofluorocarbons (CFCs) is prohibited due to environmental concerns regarding stratospheric ozone depletion. Identifying other blowing agents to replace CFCs with equal effectiveness is an ongoing challenge. Other blowing agents have been developed as alternatives to CFCs, including hydrochlorofluorocarbons (HCFCs). HCFCs are still chlorine-containing substances, but their ozone depletion potential (ODP) is lower than CFCs due to their shorter lifespan in the environment. Some other alternatives are currently available or under development. For example, CFCs may be easily replaced with hydrofluorocarbons (HFCs) that have a lower ODP than CFCs. Other alternatives include HFO (hydrofluoroolefins), FO (fluoroolefins), CFO (chlorofluoroolefins) and HCFO (hydrochlorofluoroolefins), all characterized by low ODP and GWP (Global Warming Potential) due to short lifespan in their environment. Examples include trans-1 ,3,3,3-tetrafluoroprop-1-ene or HFO-1234ze; tran-1 -chloro- 3,3,3-trifluoropropene or HCFO-1233zd; 2,3,3,3-tetrafluoropropene or HFO-1234yf, mixtures thereof, and similar structures.

In the preferred embodiment of the invention, only water is preferred as the blowing agent, and the amount of water is more than 15% by weight of the component B. In the preferred embodiment of the invention, 100% by weight of the total amount of the blowing agent consist of water. In another aspect of the present invention, the composition of the blowing agent may contain water in amounts ranging from 50 to 95% by weight. In the present invention, the amount of the blowing agent is in the range of 15-35% by weight of component B, preferably 17-28% by weight of component B.

Catalyst

The low-density semi-rigid polyurethane foam (SRPUR) with no emission or reduced emission has traditionally been made by using strong blowing catalysts such as bis- (dimethylaminoethyl)-ether (available as BDMAEE or DABCO®BL11) or pentamethyl diethylenetriamine (available as PMDETA or under the tradename POLYCAT 5). However, high levels of amine emissions occur during and after foam application, as large amounts of catalyst are required to react water with isocyanate in the blowing process. These emissions are a safety hazard, as the workers exposed to volatile amines may develop a medical condition known as 'glaucopsia', which is characterized by a temporary visual impairment. Workers' exposure to amines may be severe during the spraying of the confined spaces due to the lack of adequate ventilation. Exposure to amines can also occur during use of the house after spraying.

In order to eliminate these risks, the present invention provides the SRPUR with no emission and/or reduced emission, which has a reactivity of DABCO®BL11 due to a catalyst and/or a catalyst combination and reduces the probability of occurrence of glaucopsia (temporary blue-gray and/or blurred vision) in the formulator, practitioner, and/or end user.

In the formulation of the invention, the catalysts with no emission and/or reduced emission may be used alone or in combinations at varying rates. The principal examples of the catalysts with no emission or reduced emission are:

N,N-bis(3-dimethylamino-propyl)-N-(2-hydroxypropyl) amine; bis-(N,N- dimethylaminopropyl)amine; N,N,N-tris-(3-Dimethylaminopropyl)amine; dimethylethanolamine; dimethylaminopropylamine (DMAPA); N,N,N'- trimethylaminoethyl-ethanolamine; N,N-dimethylaminopropyl-N'-methyl-N'-(2- hydroxyethyl)amine; N,N-dimethyl-N',N'-bis(2-hydroxypropyl)-1 ,3-propylenediamine;N'- [3-(dimethylamino)propyl]-N,N-dimethylpropane-1 ,3- diamine; 2-(2-dimethylaminoethoxy)ethanol; 6-dimethylamino-1 -hexanol; 2-[[2- (dimethylamino)ethyl]methylamino]ethanol; 2-[N-(dimethylaminoethoxyethyl)-N- methylamino]ethanol; dimethylaminopropyl urea; bis(dimethylaminopropyl)urea; N- methyl-N-2-hydroxypropyl-piperazine; bis(dimethylamino)-2-propanol; N,N,N'-trimethyl- N'-3-aminopropyl-bis(aminoethyl)ether; N-(3-aminopropyl)imidazole; N-(2 hydroxypropyl)imidazole.

Trademarks of these may include ZF-10, LE-60, LE-425, DPA, ZR-50, LED-204 (HUNTSMAN); Niax EF-705, EF-708, EF-708 (MOMENTIVE); DABCO® NE300, DABCO® NE310, DABCO® MB20, POLYCAT® 31 , POLYCAT® 37, POLYCAT® 140, POLYCAT® 142, POLYCAT® 143, POLYCAT® 203, POLYCAT® 218, POLYCAT® 9, POLYCAT® 15, DABCO® T, DABCO® DMEA, POLYCAT® 17, DABCO® NE1070, DABCO® NE1080 (EVONIK).

In the preferred embodiment of the invention, Polycat 140 and/or Polycat 31 are used as the catalyst with no emission or reduced emission. The catalyst package of the present invention, consisting of Polycat 140 and/or Polycat 31 , is designed to provide the effective reactivity provided with only DABCO® BL11 or with DABCO® BL11 and Polycat 5. The catalyst package determined in the present invention makes it possible to provide a phase stabilization throughout the shelf life of the component B, which may be achieved with DABCO® BL11 at high contents of water. The amount of the catalyst with reduced emission used in the present invention is in the range of 2-15%, preferably 5-10%, by weight of the component B.

Surfactant

As the reaction of low-density semi-rigid polyurethane foam (SRPUR) occurs very fast, appropriate surfactant and/or surfactant combinations provide the desired regularity and opennes of the cell structures (for example, a polyurethane foam with a small regular cell structure containing more than 90% open cells) in order to ensure foam cell stability. Surfactants suitable for use in the SRPUR formula are generally silicone polyether copolymers and provide a good foam cell stability during foam formation, preventing shrinkage and collapse in the foam. Examples of suitable silicone surfactants include, but are not limited to, polyalkylsiloxanes, polyoxyalkylene polyol modified dimethylpolysiloxanes, alkylene glycol modified dimethylpolysiloxanes, or any combination thereof.

Examples of silicone surfactants that can be used alone or in combination within the scope of the present invention are, as products from EVON IK, TEGOSTAB® B 8408, TEGOSTAB® B 8460, TEGOSTAB® B 8450, TEGOSTAB® B 8486, TEGOSTAB® B 8487, TEGOSTAB® B1048, TEGOSTAB® B 8526, TEGOSTAB® B 8523, TEGOSTAB® B8580, TEGOSTAB® B 8870, TEGOSTAB® B 8409, TEGOSTAB® B 8453, TEGOSTAB® B 8444, TEGOSTAB® B 8443, TEGOSTAB® B 84701 , TEGOSTAB® B 84704, TEGOSTAB® B 84710, TEGOSTAB® B 84711 , TEGOSTAB® B 84712, TEGOSTAB® B 84715, TEGOSTAB® B 84718, TEGOSTAB® B 84721 , DABCO® LK 221 E, DABCO® LK 443. Again, AddSil-5596, AddSil-5598, AddSil- 5662, AddSil-5608 surfactants belonging to AddSil, the trademark of SISIB SILICONES, may be preferred within the scope of this invention. L-5348, L-5340, L-5352, L-6884, L- 6884, L-6265, L- 6189, L-5388, L-6164, L-6186, L-6188, L-5360, L-3001 , L-311 1 , L-3002, L-3222, L- 3639, L-36395, L-3415, L-3416, L-3417 surfactants belonging to Niax™, the trademark of 5 MOMENTIVE may be again used within the scope of the invention.

In the preferred embodiment of the invention, TEGOSTAB® B 84701 , a non- hydrolyzable polyether polydimethylsiloxane copolymer, is used as the surfactant. TEGOSTAB® B 84701 provides the formation of small regular cell structure in the low density SRPUR production by the effective stabilizing characteristic thereof in the current formula design where a high amount of reactive polyols and water are used. The use of surfactant in the present invention is in the range of 0.02-4%, preferably 0.5-1 .5% by weight of the component B.

Flame retardant

Phosphorus-based materials such as tris (chloroisopropyl) phosphate (TCPP) are generally used in the production of the low-density semi-rigid polyurethane foam (SRPUR) and provide a flame retardant effect, improving the non-flammability properties of the foam.

Flame retardants that can be used in the invention are not limited to TCPP, but the principal examples are tricresyl phosphate (TCP), tris (2-chloroethyl) phosphate (TCEP), tris (p-t-butylphenyl) phosphate (TBPP), tris(1 ,3-dichloro-2-propyl) )phosphate (TDCPP), isopropylphenyl diphenyl phosphate, triphenyl phosphate (TPP), isopropylated triphenylphosphate (IPTPP), tetrakis(2-chloroethyl)dichloroisopentyl diphosphate. Melamine, expandable graphite, ammonium polyphosphate (APP), pentabromodiphenyl ether, tribromoneopentyl alcohol, oligomeric ethyl ethylene phosphate, oligomeric phosphonate polyol, di(2-ethylhexyl) tetrabromophthalate (TBPH), diethyl bis(2- hydroxyethyl)aminomethylphosphonate, di(2- ethylhexyl) tetrabromophthalate (TBPH) are among the examples.

In the embodiment of the present invention, the preferred flame retardant agent is TCPP, and it is used in the range of 4% to 35%, preferably 12% to 25%, by weight of the component B formulation.

Isocyanate

Polyisocyanate is a compound or a mixture of compounds, each having at least two isocyanate (NCO) functional groups per molecule. The polyisocyanates used in the preparation of polyurethane foams are selected from aliphatic, cycloaliphatic and aromatic polyisocyanates and the combinations thereof. The NCO index is determined by dividing the actual amount of polyisocyanate used by the amount of stoichiometric polyisocyanate theoretically required to react with all the active hydrogen in the reaction mixture and multiplying by 100, and is expressed by the equation: Isocyanate Index = (Eq NCO/ Eq active hydrogen)x100

Any suitable isocyanate may be used in the present invention. Prepolymers of polyisocyanates partially pre-reacted with a polyether or polyester polyol may also be used. Examples of suitable isocyanates include at least one member selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate (TDI), diphenyl methane diisocyanate isomers (MDI), hydrated MDI, 1 ,5-naphthalene diisocyanate. Polyisocyanate consists mainly of MDI or mixtures of MDIs. In another aspect, 2,4-TDI, 2,6-TDI and mixtures thereof may be used in the present invention. TDI/MDI mixtures may also be used. Other suitable mixtures of diisocyanates may include, but are not limited to, those known in the art as crude MDI or PAPI, which includes 4,4'-diphenylmethane diisocyanate together with other isomeric and similar higher polyisocyanates.

In the preferred embodiment of the invention, polymethylene polyphenylisocyanate (polymeric MDI) is used. Polymeric MDI is a 4,4' diphenylmethane diisocyanate (MDI) based polymeric isocyanate containing oligomers and isomers having a high functionality and is a dark liquid product. The NCO content of polymethylene polyphenyl isocyanate is 31 -32% g/100 g and the NCO functionality thereof is 2.6-2.8. In the present invention, the low density SRPUR is produced with an NCO index generally in the range of 20 to 100, preferably 30 to 60. The amount of isocyanate used in the embodiment of the present invention is in the range of about 30 to 80% by weight of the total foam formulation. The preferred use of isocyanate is in the range of 40% to 60% by weight of the total foam formulation. The weight ratio of component A / component B used in the embodiment of the present invention varies between 0.8-2, preferably in the range of 1 .05-1 .4.

Other additives

In the production of the low density semi-rigid polyurethane foam (SRPUR), different optional additives may be used in the foam formulation to regulate the end-use properties of the foam product. Suitable additives may be included in the component A (isocyanate) or are usually added to the component B (polyol). In the preferred embodiment of the present invention, the additives are, but not limited to, cell openers, chain extenders, crosslinkers, fillers, pigments, epoxy resins, acrylic resins, viscosity modifiers/reducers, plasticizers or any combination thereof. The amount of these additives may be between 0-20% by weight of the total amount of the component B. In another aspect of the present invention, it is obvious that other raw materials or materials known in the art are within the scope of the present invention and may be included in the foam formulation. In the preferred embodiment of the invention, only water may be used as a blowing agent in the preparation of the component B, and it is possible to produce the low density SRPUR with similar properties using combinations of physical blowing agents such as water and hydrocarbons. In this case, it is possible to obtain an appropriate reaction profile and a regular foam cell structure by choosing the appropriate catalyst and surfactant package. It is also possible to prepare a stable component B with a shelf life of more than 12 months by adding 1 -3% of alkyl alcohol ethoxylates and/or other emulsifiers, the other damages of which are reduced, as a compatibilizer to the formula of the invention.

The production method of the low density semi-rigid polyurethane foam of the invention is as follows:

Preparation of the polyol (B) component: Polyol 1 , polyol 2, a flame retardant, a blowing agent, a catalyst and a silicone surfactant are added into a container and mixed at a mixing speed of 500-2000 rpm to obtain a premix. The premix is mixed at 10-45 °C, at a mixing speed of 1000-2000 rpm for 0.5-5 minutes. Then, the blowing agent and water are added to the mixture at a mixing speed of 500-2000 rpm and mixed. After addition, mixing is continued for 0.5-60 minutes at a speed of 1000-2000 to obtain a homogeneous and clear component B in liquid form.

Production of low density SRPUR: The resulting component B and component A consisting of isocyanate are taken into separate chambers of the high pressure machine (the temperature varies between 30-55°C in the hose lines where the components A and B are transported before mixing). The component A and the component B are impinged at a ratio of 0.8:1 .0 - 2.0:1 .0 by weight, preferably 1 .05:1 .0 - 1.4:1.0 in a mixing head of a high pressure machine and sprayed onto a suitable surface (for example, the vertical and/or horizontal surfaces of the house) at varying thickness (2.5 cm-15 cm) and with a varying number of multiple castings ranging from 1 -5 so as to form the low density SRPUR using a foam spray gun.

Examples are given below to illustrate the invention, and the invention is not limited to the formulation raw materials/inputs and quantities specified in these examples. It is obvious that those with general knowledge of the art may develop alternatives with many different modifications, including the use of equivalents instead of existing ones, in line with the described scope and examples of the invention. Therefore, it is intended not to be limited to examples of embodiments that will best explain the present invention, and to cover all embodiments, including the disclosures in the claims of the invention.

Examples

In the production of the low density semi-rigid polyurethane foam (SRPUR) of 6-10 kg/m ³ , a conventional typical formulation content and usage amounts of the prior art are provided in Table-1. The polyol used in the conventional formulation is generally the polyether triol commonly used in water-blown open-cell spray foam applications. The conventional polyether triol is an alkoxylated triol with a molecular weight of 4800 and an OH value of 34-37. Nonylphenol ethoxylate (NPE) and/or alkyl alcohol ethoxylate (AAE) may be used as an emulsifier (compatibilizer) and are included in the formulation as approximately 10 units. The combinations of BDMAEE and a cocatalyst, dimethylaminoethoxy ethanol (DMAEE), especially bis-(dimethylaminoethyl)- ether (BDMAEE), are used as catalysts. TCPP is used as a flame retardant, and silicone polyether copolymer is used as a surfactant. Polymeric MDI may be preferred as the isocyanate (A) component. Obtaining low densities such as 6-10 kg/m ³ is possible by using a high content of water as the blowing agent. The preferred amount of water is more than 15% by weight of the component B.

Table-1 : Conventional low density semi-rigid polyurethane foam (SRPUR) formulation

Polyol Component Preferred Usable

(Component B) Amount by Weight (%)

Polyol Conventional polyether polyol (triol) 25 - 45

Flame retardant TCPP 10- 25

Emulsifier/Compatibilizer Nonylphenol ethoxylate (NPE) and/or Alkyl 8- 15

Alcohol Ethoxylate (AAE) Catalyst BDMAEE (Dabco® BL-11 ) 7- 10

Surfactant Silicone surfactant 0.5- 3

Blowing agent Water 10- 25 Isocyanate (Component polymeric MDI 100 - 200

In order to control the suitability of the formulations developed with the present technology, which do not contain an external emulsifier and use catalyst with reduced emission, for the low density SRPUR production, a typical low-density SRPUR formulation in industrial standards prepared using the prior art (Comparative Example 1 ) is given in Table-2. The change in the phase stabilization of the component B when the formulation was prepared without using a compatibilizer was examined in Comparative Example 2. Comparison of the formulas of the present invention (Example 1 and Example 2) with comparative examples is given in Table-2.

In the comparative examples, a polyether triol with a glycerine initiator and a low (about 15% by weight) EO content, having a molecular weight of 4500-5000 and an OH number of 33-36 mg KOH/g was used as the conventional polyether polyol. In the Comparative Example 1 , an emulsifier consisting of mixtures of ethoxylated alcohol (alkyl alcohol ethoxylates) was used. In Examples 1 and 2, polyether diol and polyether triol with a high EO content were used as Polyol 1 , respectively, which enables the formulation design without the use of compatibilizers. Polyether diol is a reactive polyol with a molecular weight of 4000 and an OH number of 26-30 mg KOH/g, which is initiated with propylene glycol and copolymerized with propylene oxide and ethylene oxide. Polyether triol is a reactive polyol with a molecular weight of 4500 and an OH number of 36-40 mg KOH/g, which is initiated with glycerin and copolymerized with propylene oxide and ethylene oxide.

In Table-2, the catalyst package (Polycat 31 + Polycat 140) consisting of the same amount of catalysts with reduced emission was used to monitor the phase separation efficiency under the same conditions, including comparative examples. Again in Table 2, the same content and amount of the auxiliary polyol (polyol 2), flame retardant (TCPP) and non-hydrolyzed silicone surfactant (Tegostab B 84701 ) were used in all samples. Only water was used as the blowing agent in all the samples provided in Table-2, including the comparative examples, and the % water content of these samples was measured when they were freshly prepared and it was found to be in the range of 16.9-17.3%. Table-2: Comparison of the conventional SRPUR production formula and formulas without compatibilizers

Polyol Component Comparative Comparative Example 1 Example 2 (Component B), % Example 1 Example 2

By Weight

Conventional 30.3 39.3 polyether triol Polyol 1 (polyether 39.3 diol with a high EO content) Polyol 1 (polyether 39.3 triol with a high EO content)

Polyol 2 (polyether 12 12 12 12 polyol with an OH number of 450 mg KOH/g)

TCPP 21 21 21 21

Nonylphenol 9 not used not used not used ethoxylate (NPE) and/or Alkyl Alcohol Ethoxylate (AAE)

Polycat 31 + Polycat 9.5 9.5 9.5 9.5

140

Tegostab B 84701 1.2 1.2 1.2 1.2

Water 17 17 17 17

Total, gr 100 100 100 100

Isocyanate Component (Component A)

Polymeric MDI, gr 115 115 115 115

Percentage By 100//115 100//115 100//115 100//115

Weight (A/B) Percentage By 1 : 1 1 : 1 1 : 1 1 : 1

Volume (A/B)

Foam Properties

Cream time, sn 4 4 3 3

Curing time, sn 12 11 11 10

Foam density, kg/m ³ 8.2 8.9 8.7 8.9

Foam cell structure small, regular small, regular small, small, regular regular

Phase Stability Properties of Polyol

Phase separation in Phase Phase Phase Phase oven sample of 45 °C separation separation separation separation on day 8. on day 1 . on day 8. on day 15.

% water content of 22.1 39.7 24.6 17.1 oven sample of 45 °C

Phase separation in No phase Phase No phase No phase the sample kept at separation at 6 separation separation separation room conditions months on day 1. at 6 months at 6 months

The phase stability of the components B developed in the present invention was followed by applying an aging test at 45 °C, taking into account the approach in patent nos. WO2012021675A2 and US20180086873A1 . Component B samples were placed in an oven at 45 °C under normal ambient conditions, and phase separations were observed with regular daily checks. In prior art, the degree of phase separation was measured as the percent stability, i.e., percent stability was determined by measuring the height of the separated bottom layer against the height of the total sample. As only the visual follow-up of the phase separation will cause errors, in the present invention, the % water content of the samples was measured from the top, and the layer with the phase separation was determined by the change in the % water content.

In the Comparative Example 2 prepared with conventional polyether triol without using a compatibilizer, the phase separation occurs in a very short time compared to the Comparative Example 1 . The phase separation of the components B prepared without using compatibilizers with the EO-terminated and/or high EO content polyether polyols preferred in Example 1 and Example 2 did not occur for long periods of time so as to guarantee the commercial shelf life (6 months). The foam obtained in all provided examples, including the comparative examples, has properties suitable for the low density SRPUR structure. Reaction times such as cream and manual curing and the foam density values for all samples are very similar.

The detailed phase stability study of the formulation prepared in Example 1 by being kept in an oven at 45 °C is given in Table-3 together with the foam properties thereof. After examining the observational phase separation of the samples taken from the oven at specified intervals, a sample was taken from the upper surface of the sample and the % water content thereof was tested. A cross control of the phase separation was achieved by casting the foam with polyol mixtures in the untreated sample containers. Accordingly, the phase separation starts with fluctuation and turbidity on the surface of the polyol since day 8 of keeping the component B prepared in Example 1 in an oven at 45 °C, and the phase separation is clear on day 9. In contrast to the phase separation of Example 1 , which occurred on day 9 in an oven of 45 °C, no phase separation occurred at room temperatures for 6 months. No structural deterioration was observed in the foams cast for each day, which would adversely affect the reaction time and foam properties.

Table-3: Phase separation of Example 1 in an oven at 45 °C

Number of Days for Day 0 Day 1 Day 3 Day 6 Day 9

Keeping

Occurrence of phase no no no no There is a ^se P ^ara,ion fine phase separation at the top.

Phase stability, % 100 100 100 100 95.7

Water content (upper 16.9 16.9 16.7 17.0 25.1 phase), % Reaction profile, sn 3 // 11 3 // 11 3 // 11 3 // 11 3 // 11

Foam density, kg/m ³ 8.8 8.8 8.7 8.9 8.5

Foam cell structure small, small, small, small, small, regular regular regular regular regular

Cell collapse in foam no no no no no

Foam no no no no no contraction/shrinkage

In the formulas of the invention prepared without using compatibilizers, the other parameter affecting the polyol phase stability is the ratio of the usage amount of polyether polyol with high EO content to the total amount of TCPP and water used in the formula. Examples explaining this situation are given in Table-4 in comparison with Example 1. In Example 1 , the ratio of the amount of polyether diol (Example: 39.3 gr) to the sum of the amount of TCPP and water (Example: 38 gr) is approximately 1. In Examples 3 and 4, the amounts of TCPP and polyether diol were changed by keeping the amount of catalyst, silicone surfactant, auxiliary polyol (Polyol 2) and water constant. In Example 3, the phase separation occurred very clearly in a short time such as 2 days, while in Example 4, the phase separation was delayed to meet the shelf life.

Table-4: Formulas showing the change of phase separation properties when the component B ratios are different Polyol Component (Component B), Example 1 Example 3 Example 4 % By Weight

Polyol 1 (polyether diol with a high EO 39.3 32.3 42.3 content)

Polyol 2 (polyether polyol with an OH 12 12 12 number of 450 mg KOH/g)

TCPP 21 23 13

Nonylphenol ethoxylate (NPE) and/or not used not used not used

Alkyl Alcohol Ethoxylate (AAE)

Polycat 31 + Polycat 140 9.5 9.5 9.5

Tegostab B 84701 1.2 1.2 1.2

Water 17 22 22

Total, gr 100 100 100

Isocyanate Component (Component A)

Polymeric MDI, gr 115 115 115

Percentage By Weight (A/B) 100//115 100//115 100//115

Percentage By Volume (A/B) 1 : 1 1 : 1 1 : 1

Foam Properties

Cream time, sn 3 4 4

Curing time, sn 11 11 11

Foam density, kg/m ³ 8.7 8.9 8.5

Foam cell structure small, regular small, regular small, regular

Phase Stability Properties of Polyol

Phase separation in oven sample of Phase Phase Phase

45 °C separation on separation on separation on day 8 day 2 day 9

% water content of oven sample of 45 24.6 45.8 22.1

°C

Phase separation in the sample kept No phase Phase No phase at room conditions separation at separation on separation at

6 months day 2 6 months

Biopolyols may also be used as auxiliary polyols in the formula designed without using compatibilizers for the production of low density SRPUR. Castor oil-based biopolyol is used in the formula of the instant patent. The phase separation properties of the formula with biopolyol and the properties of SRPUR produced with this formula are provided in Table-5 together with Example 1 .

Compatibilizer is not used in these two formulas, which are the outputs of the present invention. The components B prepared from these formulas containing a catalyst package with reduced emission, a non-hydrolyzed silicone surfactant and a high amount of water remain stable throughout their shelf life without phase separation. The properties of the foams obtained from the isocyanate reaction of the components B of Example 1 and Example 5 meet the requirements of the commercial low density SRPUR. The component B is prepared depending on the quality and quantity of the selected polyols and other inputs, and by the suitable preparation methods compatible with all formula inputs. The low density semi-rigid polyurethane foam (SRPUR) has been produced with these components B by a spraying technique, which does not show any structural deformation such as contraction, shrinkage, collapse, etc., without sacrificing the mechanical strength, the dimensional stability, the low density of 6-10 kg/m ³ , etc.

Within the scope of the invention, a formulation of component B with an appropriate catalytic activity and reduced emissions has been provided in order to be used in the production of the low density SRPUR materials with cell structure that provides sound absorption and heat insulation efficiency, which formulation provides easy application for the consumers and remains stable throughout the shelf life without the phase separation. In the invention, the component B, which does not contain any external emulsifiers including harmful emulsifiers such as NPE or their NPE-free alternatives, is obtained, wherein the component B is used in the production of the fully water-blown low density SRPUR, which remains its phase stability throughout the shelf life thereof. In addition, the invention does not contain catalysts that cause emissions harmful to the manufacturer, the practitioner and the end user, or the ones with reduced emissions are used.

Table-5: SRPUR performance characteristics in Example 1 and biopolyol-containing formula

>

Polyol Component (Component B), % By Example 1 Example 5

Weight

Polyol 1 (polyether diol with a high EO content) 39.3 37.3

Polyol 2 (polyether polyol with an OH number of 12 450 mg KOH/g)

Polyol 2 (biopolyol with an OH number of 210 20 mg KOH/g)

TCPP 21 15

Nonylphenol ethoxylate (NPE) and/or Alkyl not used not used

Alcohol Ethoxylate (AAE)

Polycat 31 + Polycat 140 9.5 9.5

Tegostab B 84701 1.2 1.2 Water 17 17

Total, gr 100 100

Isocyanate Component (Component A)

Polymeric MDI, gr 115 115

Percentage By Weight (A/B) 100//115 100//115

Percentage By Volume (A/B) 1 : 1 1 : 1

Foam Properties

Cream time, sn 3 5

Curing time, sn 11 14

Foam density, kg/m ³ 8.7 8.5

Foam cell structure small, regular small, regular

Cell collapse in foam not observed not observed

Foam contraction/shrinkage not observed not observed

Open cell content, % 95.8 96.6

Compression strength, kPa 14.9 13.3

Tensile strength, kPa 23.3 22.0

Dimension stability @ 80 °C, 24 hours 0.57 0.78

Dimension stability @ 70 °C, 97% of humidity, 7 2.18 1.40 days Dimension stability @ -20 °C, 24 hours 0.57 0.36

Phase Stability Properties of Polyol

Phase separation in oven sample of 45 °C Phase No phase separation on separation on day 8 day 8

% water content of oven sample of 45 °C 24.6 17.2

Phase separation in the sample kept at room No phase No phase conditions separation at 6 separation at 6 months months

With the invention, the component B has been provided, which can remain stable for a long time (>6 months) without the phase separation, wherein the component B will facilitate the use of the practitioner without the need for any mixing process before the spray application.

It is possible to produce SRPUR with a density of 6-10 kg/m ³ , a high % of open cell content (>90%) and small regular cell structure, which has a high mechanical and dimensional strength in order to be used in the sound and heat insulation, especially in indoor applications with the reaction of the component B and component A of the invention, under appropriate spraying conditions. Also, a formulation of the component B with a biopolyol content (>20% by weight) without any phase separation throughout the shelf life has been provided in the present invention to be used in the production of the low density SRPUR.