LV13692B - Composition and method for obtaining polyurethane or polyisocyanurate foams from polyols of vegetable oils - Google Patents

Abstract

A composition is offered for obtaining polyurethane or polyisocyanurate foams from an isocyanate component and a polyol component, consisting of the following ingredients/products: polyol mixture, at least one catalyst, blowing agent, foam stabiliser, water, and flame retardant. The characteristic feature of the composition is that the polyol mixture consists of a vegetable oil polyol (a), for whose obtaining the oil is chosen from the group: castor, rapeseed, sun-flower, linseed, soya, palm, olive or coconut oil, wherein the component (a) is synthesised from the vegetable oil and diethanolamine; hydrophilic oxipropylated and/or oxiethylated polyalcohol (b); glycerol or triethanolamine (c). The amount of the above components in the composition, weight %, in terms of the sum of the above components (a) (b), (c): vegetable oil polyol (a) - from 55 to 95; the above polyalcohol (b) - from no 0 to 45; component (c) - from 0 to 20, while the water content in the polyol component is from 0.5 to 6.0 part by weights per 100 part by weights of the polyol mixture; in this case, the sum of the components (b) and (c) is from 2.5 part by weights to 60 part by weights per one part by weight of water, wherein water is introduced together with a HFC or HCFC type blowing agent. The polyols synthesised from the vegetable oil have a specific range of essential characteristics: the amount of higher fatty acids C8 - C22 diethanolamides and their amines as well as the number of their mono- or diglycerides, hydroxyl number, amine number, and polyol water solution pH. A method for obtaining polyurethane or polyisocyanurate foam using the above composition is also offered, and the use of the obtained foam for applying thermal insulation by the spraying method, especially to outdoor surfaces of buildings, ensuring good mechanical properties of the heat-insulating layer, a high (from 91 to 96%) closed cell content and a low water absorption as well as a good adhesion with the metal surface.

Description

COMPOSITIONS AND METHODS FOR THE EXTRACTION OF POLYURETHANE AND POLYISOCYANURATE FOAM PLASTICS FROM VEGETABLE OILS

DESCRIPTION OF THE INVENTION

The present invention relates to the production of rigid polyurethanes and polyisocyanurate foams from a polyisocyanate component and a long-term storage stable and homogeneous polyol component comprising a polyol synthesized by the trans-amidation of vegetable oil with diethanolamine.

Known state of the art analysis

It is known that polyurethane and polyisocyanurate foams are widely used as heat insulation materials for the construction of building panels, pipe insulation, refrigerator manufacturing, and on-site insulation of building structural elements [G. Oertel, Polyurethane Handbook, Hanser Publishers, Munich, Vienna, New York, 1987], Polyurethane and polyisocyanurate foams are obtained by casting and spraying equipment by mixing the polyol component with the isocyanate component in defined proportions. The polyol component consists of one or more polyols, an antifoaming agent, a foam stabilizer, a catalyst and, if necessary, also contains a fire retardant and the like. additives.

Polyurethane and polyisocyanurate foams are mainly obtained from polyether or polyester type polyols having a functionality greater than or equal to 2. The polyols, when reacted with a polyisocyanate component, form a polyurethane or polyisocyanurate foam polymer matrix.

Various tertiary amines, potassium octoate or potassium acetate or organic tin catalysts are mainly used as catalysts for the production of polyurethane and polyisocyanurate foams.

The purpose of the foam stabilizers is to facilitate the mixing of the polyol component and the isocyte component and the pore stabilization during the foaming process, and polydimethylsiloxane block polymers are commonly used for these purposes.

Water, when reacted with isocyanate composite, releases carbon dioxide, which acts as a foaming agent. HFC or HCFC type foaming agents rapidly evaporate as a result of the heat released by the reaction of the isocyanate component with polyols or water and also by the cyclotrimerization reaction of the isocyanate groups.

Flame retardant additives regulate the burning rate of polyurethane and polyisocyanurate foams due to flame exposure.

By varying the polyol components in the polyol blend, there is ample opportunity to alter the physical and mechanical properties of the polyurethane or polysocyanurate foam.

There is a growing interest in obtaining polyurethane foams from renewable raw materials, of which vegetable oils play an important role [K. Hill, Fats and oil as oleochemical raw material, Pure Appl. Chem., 2000, Vol.72, pp.1255-1264], Such interest in vegetable oils is technically and economically justified, as many polyols synthesized from vegetable oils are cost competitive with those derived from petrochemical starting materials. The use of vegetable oil polyols for the production of polyurethane foams provides an opportunity to impart new properties to these materials [M. Crank, M. Patel, Techno-Economic of Large-Scale Production of Biobased Polymers in Europe (PROBIP), Utrecht / Karlsruhe, 2004], There are many inventions dedicated to the production of polyurethane foams from t.s. oleopolols derived from epoxidized vegetable oils, but most oleopolols are characterized by low hydroxyl values (150 to 250 mg KOH / g). For this reason, for example, rigid polyurethane foams derived from soybean oil oleopolyols, when foamed with CFCs or HCFCs, tend to shrink [U.Javni, W.Zhang, ZSPetrovich, Soy-oil-based polyisocyanurate rigid foams, Jornal of Polymer and the Environment, 2004, V 12, N3, p.123]. For this reason, these polyols have become more widely used only in the production of flexible polyurethane foams.

Castor oil is similar in chemical structure to oleopoliols but also has low hydroxyl values (165 ± 5 mg KOH / g) and is therefore not used as a base polyol in polyol blends for the production of rigid polyurethane foams. However, castor oil is used as an excellent solubilizer. In the inventions described in U.S. Pat. No. 5,688,835 and WO9612759, castor oil added to a blend of polyols makes it possible to obtain homogeneous polyol components when npentane, iso-pentane or cyclopentane are used as blowing agents.

US 4237237 describes an invention for the production of hydrophobic polyurethane foams with an open pore structure and a density of 4 to 15 g / l which are well absorbed by oils. To this end, it is proposed to use polyol in the blend of polyols, which is synthesized from oleic acid and diethanolamine known as Luprintan HDF, a BASF product.

US5859078 and US5910515 propose the use of "soyamidu dea", also known as "Lincamid DSO" and identified by CAS N 68425.47.8, as a solubilizer for the production of n-pentane, isopentane and cyclopentane foamed polyurethane and polyisocyanurate foams. This product is widely known as an ingredient in shampoos and detergents. According to these inventions, up to 40% by weight of "soyamids dea" are added to the blend of polyester and / or polyether polyols to produce a homogeneous polyol component containing as antifoaming agents n-pentane, isopentane or cyclopentane. However, these inventions have the following disadvantages:

- 'soyamids dea' is not a product which could be identified as a polyol for the production of polyurethane materials, as it does not have a hydroxyl value;

- the characteristics shown for this product indicate that it has a very high content of free diethanolamine of up to 9,5% by weight;

- highly flammable foaming agents are used: n-pentane, isopentane and cyclopentane; therefore, as polyol components, they are little suited to the production of polyurethanes and polyisocyanurate foams by spraying.

Vegetable oil amides as detergent additives are also produced from other vegetable oils, but their characteristics are slightly different from 'soyamids dea'. For example, the amount of free diethanolamine CDE 6501 in coconut oil diethanolamide is even higher.

US 6075064 describes the production of water-foamable hydrophobic polyurethane foams from OH-containing polyols of C9-C22 fatty acids, triglycerides of OH-groups and sorbitan esters of higher fatty acids. However, the description of the invention is incomplete - it does not even contain data on the content of the closed pores of the foam obtained and their mechanical properties and therefore it is not possible to adequately evaluate the properties of these materials. Nor does the disclosure disclose any storage stability for such polyol components. It is highly likely that the low-OH OH-free polyolefins in the polyol blend form an emulsion in the presence of water as an antifoaming agent. This factor could make it difficult to use the invention described in U.S. Patent No. 6,075,064, especially where thermal insulation has to be obtained "in situ" by spraying equipment.

The formation of stable polyol components from vegetable oil polyols has the problem of using wholly or partially water as a foaming agent. The problem lies in the fact that vegetable oil polyols are very hydrophobic products, and even small amounts of water are added to form an emulsion. It has been experimentally proven that a polyol component containing vegetable oil polyol and only water is used as the foaming agent, in all cases it collapses during foaming of the polyurethane foam.

One of the prerequisites for processing polyurethane or polyisocyanurate foams with casting or spraying equipment is the following: The polyol components must not undergo significant changes in the foaming parameters during several months of storage and may not form several phases.

It is an object of the present invention to provide a composition and method for producing rigid polyurethanes or polysocyanurate foams from a blend of stable and homogeneous polyol components for long-term storage, based on vegetable oils synthesized polyols and water foaming.

Summary of the Invention

The object of the invention is achieved by the use of a composition comprising an isocyanate component, a stable and homogeneous polyol component for sustained storage of a polyurethane or polysocyanurate foam composition comprising: a mixture of polyols, at least one catalyst, foaming agent, foam stabilizer, water and flame retardant. wherein the blend of polyols consists of:

- vegetable oil polyol (a) having a hydroxyl number in the range of 290 to 420 mg KOH / g, preferably 310 to 420 mg KOH / g;

a hydrophilic oxypropylated and / or oxyethylated polyhydric alcohol (b) having a functionality of 3 to 8, preferably 4.5 to 6, and a hydroxyl number in the range of 300 to 650, more preferably 400 to 650 mg KOH / g;

- glycerol or triethanolamine (c), with:

- component (a) in the polyol blend is from 55 to 95% by weight, preferably from 60 to 90% by weight, based on the sum of components (a), (b) and (c);

component (a) is synthesized from vegetable oil and diethanolamine at a molar ratio of 2.05 to 2.95, preferably 2.10 to 2.70;

- component (a) is a polyol from rape, sunflower, linseed, soybean, palm, olive, coconut or castor oil;

- the vegetable oils polyols contained in the composition have the following characteristics, expressed as a percentage by weight:

• higher fatty acids Cg - C22 diethanolamides and amines 66 to 82;

• Cg-C ₂₂ mono- or diglycerides of higher fatty acids, from 11 to 32;

• the hydroxyl number (mg KOH / g) is between 290 and 420 • the amine number (mg KOH / g) is between 6 and 18;

Glycerol from 1 to 4, with 1% polyol aqueous solution having a pH of 8.6 to 9.2 and

- the content of component (b) in the polyol mixture is from 0 to 45% by weight, preferably from 20 to 45% by weight, based on the sum of the components (a), (b) and (c).

component (c) is from 0 to 20% by weight, preferably from 5 to 10% by weight, based on the sum of components (a), (b) and (c);

the water content of the polyol component is from 0.5 to 6.0 parts by weight, preferably from 1.0 to 4.0 parts by weight, per 100 parts by weight of the polyol mixture;

the sum of components (b) and (c) is from 2.5 parts by weight to 60 parts by weight, preferably from 5 parts by weight to 30 parts by weight, per part by weight of water;

- the water in the polyol component is in combination with a foaming agent of the HFC or HCFC type, wherein the water is first mixed in component (b) or component (c) before making the polyol component;

the isocyanate component has an index in the range of 100 to 400, preferably from 110 to 300, wherein the isocyanate component is a polyisocyanate having a functionality of 2.3 to 3.0, more preferably 2.6 to 3.0.

Component (a) is synthesized by trans amidating the selected vegetable oil, wherein the molar ratio of vegetable oil to diethanolamine is selected to be 1: (2.05 to 2.95), preferably 1; (2.1 to 2.7). The following vegetable oils are used for transamidation: castor, rapeseed, sunflower, soybean, coconut and olive oil. The synthesis is carried out at 130-150 ° C. Higher synthesis temperatures are not recommended because of the potential intracellular cyclization of diethanolamine resulting in piperazine derivatives. Zinc acetate or lithium hydroxide in an amount of 0.1 to 0.3% by weight of vegetable oil and diethanolamine is proposed as transamidation catalysts. The described synthesis process meets the criteria of "green chemistry" as it does not produce by-products or harmful emissions. Basically, the proposed synthesis of the final product are vegetable oils falling within the higher saturated and unsaturated fatty acids, Cg-C ₂₂ amide to an amine, mono-, diglycerides and glycerol mixture. As the trans-amidation process of vegetable oil is accompanied by trans-esterification, the final product includes the amides (1) of the highest fatty acids and their amines (2) having the following structure:

R-C-N <j • CH ₂ CH ₂ OH CH ₂ CH ₂ OH

HN <^, CH ₂ CH ₂ OH ch ₂ ch ₂ —O (1)

However, the content of compound (2) in the final product is small, as indicated by the amino acid values, since the transamidation process is easier than the transesterification process.

Polyols synthesized from vegetable oils have an average functionality in the range of 2.0 to 2.3 and increase with increasing molar ratio of diethanolamine to vegetable oil. An exception is the polyol obtained by transamidating castor oil, which has an average functionality of 2.7 to 3.0 at the molar ratio of diethanolamine. The synthesis prerequisites described above make it possible to obtain polyols having hydrosilic values of 290 to 420 mg KOH / g and meeting the requirements for the use of the resulting polyols as basic polyols in blends of solid polyurethanes or polyisocyanurate foams. Synthesized polyols include t.s. "Soft polyols", which means that they reduce the brittleness of the resulting foam. Unlike soyamida dea and similar products which are manufactured as detergent additives, the synthesis of polyols by the present invention, by transamidating vegetable oils, ensures that the resulting polyols are more suitable for the production of polyurethane grade materials, since the hydroxyl number values of the polyol and the polyol does not contain free diethanolamine. Experimentally it was found that when the polyol is high in free diethanolamine, it reacted with the flame retardant trichloropropyl phosphate to be added to the polyol component and at room temperature the content of diethanolamine in the polyol component decreased by 13% by weight. As a result, the pH of the polyol component also decreases and the foaming parameter values increase. This fact strongly suggests that products made from vegetable oils and diethanolamine for use in detergents are not well suited to polyurethane chemistry and technology because of their high content of free diethanolamine.

By means of the vegetable oil polyols described in the invention, the polyurethane or polyisocyanurate foam polymer matrix can introduce the higher saturated and unsaturated fatty acid Cs-C? This fact is the reason behind these foam polymer matrices, i.e. for intra-molecular plasticization. The polyols described in the present invention are very suitable for the production of water-foamable polyurethane or polysocyanurate foams because of the intrinsic plasticity of the foam which prevents the formation of foam and the use of the above-mentioned vegetable oils-synthesized polyols as polyol blends has a small brittleness and good adhesion to the metal construction surface.

The objective of providing stable and homogeneous storage components of polyol based on vegetable oils polyols is achieved even if hydrophilic polyols are also used in the polyol blend, but the condition is that the blowing agent (water) at 20-30 ° is prepared before the polyol blend is prepared. C must be mixed with hydrophilic polyol, glycerol and / or triethanolamine until homogeneous. After this operation, the resulting mixture should be added to the vegetable oil polyol, mixed to a homogeneous condition, and then the other ingredients of the polyol component added and homogenized. If this condition is not met, but when water is added to the vegetable oil polyol or polyol component, it is found that the resulting polyurethane or polysocyanurate foam has a very low closed-cell pore content (7 to 35%) and has a high content (0.5 to 1.0 mm) pore inclusions.

The present invention provides the use of oxypropylated and / or oxyethylated polyols synthesized from polyhydric alcohols: sorbitol, sucrose, glucose, pentaerythritol, glycerol or trimethylolpropane, preferably having a hydroxyl number of from 300 to 300, as hydrophilic polyols for storage of a stable polyol component. 650 mg KOH / g. Since the synthesized vegetable oil polyols have low functionality, preference is given to sorbitol, glucose or sucrose synthesized polyether polyols having a functionality of 4.5 to 6. If a polyhydric alcohol is used as the hydrophilic polyol, the amount of the polyol blend is may contain from 5 to 20% by weight. The amount of glycerol in the polyol blend should not exceed 10% by weight, since higher amounts of the polyol blend allow for phase separation, but the polyol component of the invention maintains homogeneity at 10 ° C and no phase separation is observed.

In addition to water, other foaming agents such as: HFC-365mfc, HFC227ea, HFC-134f, HCFC-141b or mixtures thereof may be used to produce the polyurethane or polyisocyanurate foams of the invention. traditional foaming agents.

Well-known tertiary amines such as dimethyl ethanolamine, dimethylcyclohexylamine, dimethylpiperazine, pentamethyl diethylenetriamine, triethylenediamine and the like can be used as catalysts for carrying out the invention. Tertiary amine type catalysts can be used in combination with isocyanate group trimerization catalysts such as potassium acetate solution in diethylene glycol or potassium octate. As strong gel catalysts, tin octate, tin dibutyl dilaurate and the like can be used. catalysts of this class.

Known dimethylsiloxane block polymers, such as: Tegostab B 8870, ΝΙΑΧ Silicone L-6100, etc., in the range of 0.5 to 2.5 parts by weight per 100 parts by weight of a polyol mixture, are recommended for use as foam stabilizers. Polyols from transamidated vegetable oils have the properties of a non-ionic surfactant and this contributes to the effective blending of the polyol component and the isocyanate component during the foaming process and also contributes to the formation of ultra-fine sponge foam.

Trichloroethyl phosphate, trichloropropyl phosphate and other phosphorus and / or chlorine-containing flame retardants may be used as the flame retardant in the polyol component, but it is preferable to use trichlopropyl phosphate in order not to substantially alter its original activity during prolonged storage.

The crude diphenylmethane diisocyanate, known as polyisocyanates in the polyurethane technology, having a functionality of 2.3 to 3.0, preferably 2.6 to 3.0, can be used as the isocyanate component. In order to use the polyurethane or polyisocyanurate foams of the compositions of the invention, the isocyanate index values should be between 100 and 400, preferably between 110 and 300.

Examples of realization of the invention

Example 1:

In a 1.0 liter flask equipped with a stirrer and a reflux condenser, weigh 352 g (0.40 mol) of rapeseed oil with a saponification index of 174 mg KOH / g, heat to 140 ° C under inert atmosphere and add 1.42 g of catalyst (zinc acetate) and 105 g (1.0 mol) of molten diethanolamine heated to 70 ° C are added over 15 minutes. After

2.5 hours of transamidation yields a polyol having a hydroxyl number of 354 mg KOH / g, an amine number of -12.3 mg KOH / g, pH 9.1, water content 0.27 wt% and a viscosity of 670 mPa.s at 25 °. C. Made of the following polyol components: Synthetic rapeseed oil polyol - 80 parts by weight, Oxypropylated glycerol (Lupranol 3300, BASF) with hydroxyl number 420 mg KOH / g - 2.0 parts by weight, Water - 4.5 parts by weight, Tegostab B8870 - 1.5 parts by weight, dimethyl ethanolamine 5.0 parts by weight, 30% potassium acetate solution in diethylene glycol 2.0 parts by weight, trichloropropylphosphate 30 parts by weight.

The polyol component is prepared by first mixing the water with Lupranol 3300 until homogeneous and then adding the mixture to the rapeseed oil polyol and homogenizing again. The other ingredients of the composition are added to this mixture and homogenized. The resulting polyol component is a transparent single-phase product. Foaming is performed by adding 214 parts by weight of the polyisocyanate (isocyanate index -170) to the resulting polyol component. The obtained composition is characterized by the following foaming parameters: start time - 8 (11) s, gel time - 18 (20) s, adhesion time 25 24 (28) s. The values of the foaming parameters after the polyol component at 6 months storage temperature are shown in brackets.

The resulting foam density is 33.2 kg / m ³ , closed pores content 91.0%, water absorption after 7 days 2.7 V%, compressive strength 0.13 MPa, modulus of elasticity 3.6 MPa, flammability spreader according to DIN 4102 - Class B.

Example 2:

Weigh 560 g (0.64 mol) of sunflower oil, 191 mg KOH / g, heat to 140 ° C in a 1.0 liter flask equipped with a reflux condenser and a stirrer, and add 1.95 g of catalyst (zinc) acetate) and then 141 g (1.34 mol) of molten diethylamine heated to 70 [deg.] C. are added under stirring over 15 minutes under an inert atmosphere. After 2 hours of transamidation, a polyol having a hydroxyl number of 310 mg KOH / g, an amine number of -11.5 mg KOH / g, pH 8.70, a water content of 0.22% and a viscosity of 477 mPa.s at 25 ° is obtained. C.

Made of the following polyol component: Synthetic Sunflower Oil Polyol - 70 parts by weight, Oxypropylated sorbitol (Daltolac R475, Huntsman) with hydroxyl number 470 mg KOH / g - 20 parts by weight, Triethanolamine - 10 parts by weight, Water - 1.0 parts by weight, Foam stabilizer Tegostab B8870 - 1.5 parts by weight, dimethylcyclohexylamine 4.0 parts by weight, 30% potassium acetate solution in diethylene glycol - 1.5 parts by weight, foaming agent HCFC-141b - 25 parts by weight, dibutyl dinurate tin - 0.2 parts by weight, trichloropropylphosphate - 25 parts by weight. The polyol components are prepared by first mixing the water with Daltolac R 475 and triethanolamine and then adding it to the sunflower oil polyol and homogenizing again. The other ingredients of the composition are added to this mixture and homogenized. The resulting polyol component is a transparent single-phase product. To the resulting polyol component is added 167 parts by weight of the polyisocyanate (isocyanate index - 150). The resulting foam composition is characterized by the following foaming parameters: start time - 8 (10) s, gel time - 20 (24) s, adhesion time - 27 (32) s. The resulting foam density is 39.0 kg / m ³ , closed pores content 91.0%, water absorption after 7 days - 2.9 V%, compressive strength 0.17 MPa, elastic modulus 4.6 MPa, flammability index according to DIN 4102 - Class B.

Example 3:

The polyol component of polyurethane foam is prepared as follows: sunflower oil polyol 75 parts by weight as described in Example 2, oxypropylated sorbitol polyether polyol (Lupranol 3422, BASF) with hydroxyl number 490 mg KOH / g - 20 parts by weight, glycerol 5.0 parts by weight, water - 1.0 parts by weight, Tegostab B8870 foam stabilizer - 1.5 parts by weight, pentamethyl diethylenetriamine - 6.0 parts by weight, potassium acetate 30% solution in diethylene glycol - 2.0 parts by weight, foaming agent HCFC 141-b 30.0 parts by weight , dibutyl tin laurate tin - 0.2 parts by weight, trichloropropyl phosphate - 33 parts by weight.

The polyol components are prepared by first mixing the water with Lupranol 3422 and glycerol and then adding it to the sunflower oil polyol and homogenizing again. Other components of this polyol component are added to this mixture and homogenized. The resulting polyol component is a transparent, single-phase product and is added to 197 parts by weight of a polyisocyanate (isocyanate index 170). Said polyol component is homogeneous during 6 months storage at 10 ° C and has the following foaming parameters: start time 5 (6) s, gel time 10 (11) s, adhesion time 12 (14) s . The polyol component has a density of 1.09 g / cm ^J and a viscosity of 95 mPa · s and is suitable for processing in a high pressure spray machine at a 100: 100 volume ratio of said component to a polyisocyanate. The density of the foam produced by high pressure spray equipment is 38.1 kg / sealed pore content 96.5%, water absorption after 7 days - 3.1% V, compressive strength - 0.17 MPa, elastic modulus - 4.7 MPa, flammability index according to DIN 4102 - class E. The foam is good adhesion to the surface of metal structures.

Example 4

Weigh 396 g (0.45 mol) of soya bean oil, 189 mg KOH / g, warm to 140 ° C in a 1.0 liter flask equipped with a reflux condenser and a stirrer, add 1.35 g of catalyst (lithium) hydroxide) and 127 g (1.22 moles) of molten diethylamine heated to 70 ° C are added over 15 minutes with stirring under an inert atmosphere. After 2 hours of transamidation, a polyol having a hydroxyl number of 375 mg KOH / g, an amine number of 15.1 mg KOH / g, pH 8.95, a water content of 0.32% and a viscosity at 25 ° C is obtained.

- 486 rnPa-s. Made of the following polyol component: Synthetic soybean oil polyol - 60 parts by weight, Oxypropylated sorbitol polyether polyol (Lupranol 3422, BASF) with hydroxyl number 490 mg KOH / g - 35 parts by weight, Glycerol - 5.0 parts by weight, Water

- 2.0 parts by weight, Tegostab B8870 foam stabilizer - 1.5 parts by weight, dimethylcyclohexylamine - 3.0 parts by weight, 30% potassium acetate solution in diethylene glycol

- 1.0 parts by weight, foaming agent Solkane 365mfc / 227ea - 20 parts by weight, trichloropropyl phosphate - 33 parts by weight. The polyol component is prepared by first mixing the water with Lupranol 3422 until a homogeneous state with glycerol is added to the soy oil polyol and homogenized again. The other ingredients of the composition are added to this mixture and homogenized. To the resulting polyol component is added 177 parts by weight of the polyisocyanate (isocyanate index - 115) The resulting polyol component is a transparent single phase product and is characterized by the following: start time - 12 (14) s, gel time - 31 (35) s, stickiness time - 45 (50) s. Obtained fine-cellular foam density - 47.8 kg / m ³ , closed pore content - 92.1% compressive strength - 0.24 MPa, elastic modulus 4.90 MPa, water absorption after 7 days - 2.95 V%, flammability index according to DIN 4102 - Class B.

Example 5

Weigh 440 g (0.5 mol) of rapeseed oil with a saponification index of 172 mg KOH / g in a 1.0 liter flask equipped with a reflux condenser and a stirrer, warm to 140 ° C and add 1.42 g of catalyst (zinc) acetate) and then, under stirring in an inert atmosphere, add 152 g (1.45 moles) of molten diethanolamine heated to 70 ° C over a period of 15 minutes and, after 3.5 hours of transamidation, obtain a polyol having an hydroxyl number of 410 mg KOH / g. -16.2 mg KOH / g, pH 9.10, water content 0.27% and viscosity at 25 ° C - 710 mPa.s.

Polyisocyanurate foam is made from the following polyol component: Synthetic rapeseed oil polyol - 90 parts by weight, triethanolamine - 10 parts by weight, water - 1.5 parts by weight, Tegostab B8870 - 2.5 parts by weight, dimethyl ethanolamine - 2.5 parts by weight , 30% by weight solution of potassium acetate in diethylene glycol 3.2 parts by weight, the foaming agent Solkane 365mfc / 227ea - 30 parts by weight, trichloropropyl phosphate - 40 parts by weight. The polyol component is prepared as follows: first, the water is mixed with the triethanolamine until homogeneous and then added to the rapeseed oil polyol and homogenized again. The other ingredients of this polyol component are added to this mixture and homogenized. The resulting polyol component is a transparent, single-phase product and is added to 330 parts by weight of a polyisocyanate. (isocyanate index - 300). The resulting foam composition is characterized by the following foaming parameters: start time - 16 (19) s, gel time - 32 (37) s, adhesion time - 50 (58) s. The foam obtained has the following properties: density - 47.7 kg / m ³ , closed pore content - 96.8%, compressive strength - 0.21 MPa, elastic modulus - 6.23 MPa, water absorption after 3.2 days - 3.2 V% , flammability index according to DIN 4102 - Class B. Foam has good adhesion to the surface of metal structures.

Example 6

Weigh 440 g (0.5 moles) of castor oil, 183 mg KOH / g, warm to 140 ° C in a 1.0 liter flask equipped with a reflux condenser and a stirrer, add 1.53 g of catalyst (zinc acetate) ) and 145 g (1.39 moles) of molten diethylamine heated to 70 ° C are added over 15 minutes under inert atmosphere. After

2.5 hours of transamidation yields a polyol having a hydroxyl number of 414 mg KOH / g, pH 9.15, an amine number of -12.9 mg KOH / g, a water content of 0.27% and a viscosity at 25 ° C of 2340 mPa.s. s. Prepared polyol component of the following composition: Synthesized castor oil polyol - 90 parts by weight, triethanolamine - 10 parts by weight, water - 1.0 parts by weight, Tegostab B 8870 - 1.5 parts by weight foam stabilizer, dimethyl ethanolamine - 4.0 parts by weight, potassium acetate 30% solution in diethylene glycol - 2.0 parts by weight, foaming agent Solkane 365mfc / 227ea - 23 parts by weight, trichloropropyl phosphate - 25 parts by weight.

The polyol component is prepared by first mixing the water with the triethanolamine until homogenous, and then adding the mixture to the castor oil polyol and homogenizing again. The other ingredients of this polyol component are added to the mixture and homogenized. The resulting polyol component is a transparent, single-phase product and 228 parts by weight of polyisocyanate (isocyanate index 200) is added. The foam composition is characterized by the following foaming parameters: start time -18 (22) s, gel time - 33 (38) s, adhesion time - 47 (55) s. The foam obtained has the following properties: density - 43.0 kg / m ³ , closed pores content - 94.2%, water absorption after 7 days - 3.2% V, compressive strength - 0.19 MPa, modulus of elasticity - 5, 1 MPa, flammability index according to DIN 4102 - class E.

Example 7

Weigh 484 g (0.55 mol) of rapeseed oil, 172 mg KOH / g, warm to 140 ° C in a 1.0 liter flask equipped with a reflux condenser and a stirrer, add 1.52 g of catalyst (zinc acetate) ) and 156 g (1.49 moles) of molten diethylamine heated to 70 ° C are added over 15 minutes under inert atmosphere. After 3.5 hours of transamidation, a polyol having a hydroxyl number of 385 mg KOH / g, an amine number of -15.4 mg KOH / g, pH 9.05, a water content of 0.30% and a viscosity at 25 ° C of 680 mPa.s is obtained. . Prepared polyol component of the following composition: rapeseed oil polyol - 60 parts by weight, oxypropylated sorbitol polyether polyol (Lupranol 3422, BASF) with hydroxyl number 490 mg KOH / g - 35 parts by weight, glycerol - 5.0 parts by weight, water - 3.0 parts by weight , foam stabilizer Tegostab B8870 - 1.5 parts by weight, dimethylethanolamine - 2.0 parts by weight, dibutyldilaurate tin - 0.05 parts by weight, foaming agent Solkane 365mfc / 227ea - 10 parts by weight. The polyol component is prepared by first mixing the water with Lupranol 3422 and the glycerol until homogeneous and then adding the mixture to the rapeseed oil polyol and homogenizing again. The other ingredients of the composition are added to this mixture and homogenized. The resulting polyol component is a transparent single-phase product. To the resulting polyol component is added 183 parts by weight of the polyisocyanate (isocyanate index 110) and foamed. The resulting foam composition is characterized by the following foaming parameters: start time - 20 (23) s, gel time - 31 (35) s, adhesion time - 40 (46) s. The foam obtained has the following properties: density 31.0 kg / m ³ , closed pores content 91.2%, water absorption after 7 days 3.1 V%, compressive strength 0.15 MPa, elastic modulus 4.1 MPa.

Example 8 (for comparison)

Weigh 440 g (0.5 moles) of rapeseed oil, 172 mg KOH / g, heat to 140 ° C, add 1.6 lg of catalyst (zinc acetate) in a 1.0-liter flask with stirrer and reflux condenser. ) and 110 g (1.05 mol) of molten diethylamine heated to 70 ° C are added over 15 minutes under inert atmosphere. After 2 hours of transamidation, a polyol having a hydroxyl number of 312 mg KOH / g, pH 8.69, an amine number of -10.2 mg KOH / g, a water content of 0.22% and a viscosity at 25 ° C of 605 mPa.s is obtained.

Polyurethane foam is made from the following polyol component: Synthetic rapeseed oil polyol - 100 parts by weight, water - 3.0 parts by weight, Tegostab B8870 foam stabilizer - 1.5 parts by weight, dimethyldiethanolamine - 3.0 parts by weight, 30% potassium acetate solution diethylene glycol 1.5 parts by weight, trichloropropyl phosphate 25 parts by weight. Mixing all ingredients produces a polyol component which is an unstable emulsion. A laboratory test of foaming by adding 180 parts by weight of a polyisocyanate (isocyanate index 150) to the polyol component showed that the foam collapsed and the foam collapsed before reaching the gel stage. A similar negative result was obtained by foaming other isocyanate-containing polyol components, which are synthesized from vegetable oils and water.

Example 9 (for comparison)

The polyol component of polyurethane foam is prepared as follows: rapeseed oil polyol - 95 parts by weight, triethanolamine - 5.0 parts by weight, water - 2.0 parts by weight, Tegostab B8870 - 1.5 parts by weight, dimethyldiethanolamine - 3.0 parts by weight, 30% by weight solution of potassium acetate in diethylene glycol, 1.5 parts by weight, Solkane 365mfc / 227ea - 15 parts by weight, foaming agent, 25 parts by weight of trichloropropyl phosphate. All ingredients in the polyol component are mixed at the same time. The resulting polyol component is an emulsion. To this mixture are added 180 parts by weight of polyisocyanate (isocyanate index - 160) and stir (m = 1480 rpm) for 6 s, then pour into cardboard. The foam composition has the following foaming parameters: start time -10 s, gel time - 28 s, stickiness time - 38 s. The result is a foam with an uneven pore structure, which has a significant amount of large pores (0.5 to 1.0 mm), which has the following properties: density - 33.1 kg / liter closed pore content - 7.6%, water absorption after 7 days - 3.9 V%., compressive strength - 0.14 MPa, modulus of elasticity - 3.40 MPa.

Case study

From the first seven examples, it can be seen that the patentable composition for the production of polyurethane and polyisocyanurate foams enables the storage of stable polyol components from a blend of polyols, the main component (from 55 to 95% by weight) of renewable vegetable oils. The composition of the compositions described therein for the production of polyurethane and polysocyanurate foams exhibits minor changes in start time, gel, and adhesion time after 6 months at room temperature for the polyol component. For this reason, such polyol components are advantageous for use in "in situ" conditions, especially when spray processing is envisaged. Polyurethane and polyisocyanurate foams obtained from the polyol components described in the invention, when mixed as indicated in claim 6 of the formula of the invention, are characterized by good mechanical properties, high (91 to 96%) closed pore content and low water absorption. The examples described in the invention show that blends of vegetable oils based on polyols are particularly useful for the production of polyisocyanurate foams because they reduce their brittleness, and the foams obtained have good adhesion to metal structural elements even at an isocyanate index value of 200 to 300. In the first seven examples described, foam is a hydrophobic material with a low water absorption of 2.7 to 3.2 V% after 7 days of exposure to water, and is particularly important for thermal application to objects located "below the open air". sky. "

From the comparative examples it can be seen that, without fulfilling the conditions of the invention and producing polyurethane or polyisocyanurate foams, the foam collapses during foaming or the foams obtained have a poor pore structure and low pore content.

Claims (8)

A composition for the production of a polyurethane or polyisocyanurate foam from an isocyanate component and a stable and homogeneous polyol component for prolonged storage, the composition comprising the following ingredients / products: polyol blend, at least one catalyst, foaming agent, foam stabilizer, water and flame retardant. that the polyol blend consists of: - vegetable oil polyol (a) having a hydroxyl number in the range of 290 to 420 mg KOH / g, preferably 310 to 420 mg KOH / g, wherein the vegetable oil for the production of polyol (a) is selected from the group: castor, rapeseed , sunflower, linseed, soybean, palm, olive or coconut oil; - a hydrophilic oxypropylated and / or oxyethylated polyhydric alcohol (b) having a functionality of 3 to 8, preferably 4.5 to 6, but having a hydroxyl number in the range of 300 to 650, more preferably 400 to 650, - glycerol or triethanolamine (c), wherein the composition is further characterized in that: - the vegetable oil polyol (a) is present in a mixture of 55 to 95% by weight, preferably 60 to 90% by weight, of the sum of said components (a), (b) and (c); - said polyhydric alcohol (b) is present in an amount of from 0 to 45% by weight in a polyol blend, preferably from 20 to 45% by weight, based on the sum of the weight of said components (a), (b) and (c) - glycerol or triethanolamine (c) in a polyol blend of from 0 to 20% by weight, preferably from 5 to 10% by weight, of the sum of the components (a), (b) and (c). Composition according to claim 1, characterized in that: the water content of the polyol component is from 0.5 to 6.0 parts by weight, preferably from 1.0 to 4.0 parts by weight, per 100 parts by weight of polyol wherein the sum of components (b) and (c) is from 2.5 parts by weight to 60 parts by weight, preferably from 5 parts by weight to 30 parts by weight, with one part by weight of water and water being injected with HFC or HCFC type foaming agent. Polyurethane or polyisocyanurate foam composition according to claim 1 or 2, characterized in that the vegetable oil polyol (a) is synthesized from vegetable oil and diethanolamine to a molar ratio of vegetable oil to diethanolamine, from 2.05 to 2, 95, preferably from 2.10 to 2.70. Composition according to one of Claims 1 to 3, characterized in that the polyols synthesized from vegetable oils have the following percentages by weight: - diethanolamides of the highest fatty acids Cg - C22 and their amines 66 to 82, - higher fatty acids Cs - C22 in the mono- or diglyceride range from 11 to 32, - the hydroxyl number (mg KOH / g) is between 290 and 420. - amine number (mg KOH / g) is between 6 and 18 mg KOH / g - glycerol from 1 to 4, wherein - The pH of a 1% aqueous polyol solution is between 8,6 and 9,2. A process for the production of polyurethane or polyisocyanurate foam using the composition according to any one of claims 1 to 4, characterized in that water is successively mixed with said polyhydric alcohol (b) and said component (c) until a homogeneous state is obtained. the mixture is then blended with the vegetable oil polyol (a) and after homogenization, the other ingredients of the polyol component are added to the mixture and the mixture is homogenized again. Process for the production of polyurethane or polyisocyanurate foams according to claim 5, characterized in that the isocyanate component used has an index in the range of 100 to 400, preferably 110 to 300. 10th 7. A polyurethane or polyisocyanurate foam obtained in accordance with claim 5 or 6. The use of a composition according to any one of claims 1 to 4. The use of foam according to claim 7 for applying heat insulation by spraying, in particular on surfaces of building structures under open 15 with good mechanical properties, high (91 to 96%) closed pore content and low water absorption as well as good adhesion to metal surfaces.