FI58626C - VAERMEISOLERINGSMATERIAL - Google Patents

Description

ΓβΊ tm ANNOUNCEMENT caÄ0 ^ lbj (11) utläggningsskrift boozo C (45) Patent nydnn * i ly '0 G3 1C · H ^^ (51) Kv.ik3iM.ctf C 03 C 25/02 // C 04 · B 43 / 02 FINLAND —FINLAND (21) Petenttlhekemu »- Patentaraftknlng T73Ö68 (22) HekemUpilvI - Antöknlngidif 20.12.77 (23) Alku pilvi - Glltlgheudeg 20.12.77 (41) Tullut kiikikuksi - Blivlt offentllg 21.06.79

National Board of Patents and Registration (44) Date of publication of the notice. - oft ΊΊ „

Patent and ocean registration Aneekin utitgd och uti. * Kriften pubikerad cfo.ii.ou (32) (33) (31) Privilege requested - Begird prlorltet (71) Tallinsky Politekhnichesky Institut, ulitsa Ekhitayate tee 5, Tallinn, Kievsky Kombinat Stroiindustrii Stroiindustrii 13, Kiev, USSR (SU) (72) Karl Ritsovich Kiisler, Tallinn, Tiit Karlovich Kaps, Tallinn, Peep Gerkhardovich Kristyanson, Tallinn, Jury Felixovich Vabaoya, Tallinn,

Tynu Aaduvich Kumari, Tallinn, Anne Adolfovna Tynnisson, Tallinn,

Vladimir Alexandrovich Zdon, Kiev, Eduard Mikhailovich Dolgy, Kiev,

Ivar Kharaldovich Roox, Kokhtla-Yarve, Gurgen Kazarovich Avakian, USSR (SU) (7 * 0 Oy Kolster Ab (5h) Thermal insulation material - Värmeisoleringsmaterial

The invention relates to the production of building materials and in particular heat-insulating material combinations which can be used for heating precast concrete elements, for insulating walls, roofs, pipelines and tanks.

A thermal insulating agent consisting of 85 to 98 parts by weight of mineral fibers and 15 to 2 parts by weight of a binder applied to the fibers, a modified resolifenol-formaldehyde resin based on phenol, a 50% aqueous solution of formaldehyde, disium hydride, barium hydride, is already known in the art. water and sulfuric acid. The following ratio of ingredients (by weight) is used to prepare the binder: phenol - 100% aqueous solution of formaldehyde - 154 barium hydroxide - 15 dicyandiamide - 35 2 58626 water - 24.1 sulfuric acid up to a certain pH of the skin.

The thermal insulation material containing the mineral fiber and the binder in the above composition has improved adhesion properties compared to the thermal insulation material containing sodium hydroxide in the binder combination, but the stability of the binder deteriorates over time.

The shelf life of the binder, which is a component of the above-mentioned thermal insulation material, at + 5 ° C (requires special tanks with thermostat) is 4 weeks.

Since the binder does not contain waterproofing additives, the thermal insulation material does not have water-repellent properties.

A thermal insulating agent containing mineral fibers and a binder applied thereto is a modified resolifenol-formaldehyde resin based on phenol, formaldehyde, barium hydroxide, water, urea or melamine.

Also known is a heat insulating agent comprising mineral fibers and a binder applied to the fibers which is a modified resole-phenol-formaldehyde resin based on phenol, a 37% aqueous solution of formaldehyde, dicyandiamide-propane-sodium hydroxide, boric acid addition -1100 ").

The following ingredients are used in the preparation of the binder, which is a component of the heat insulating agent: phenol - 100% 37% aqueous solution of formaldehyde - 340 dicyanide mLd - 40 sodium hydroxide - 3.7 silane "A-1100" - 0.001-2% by weight by weight of the resulting phenol-formaldehyde resin boric acid pH to skin = 7.5 to 8.0.

A modified resoliphenol-formaldehyde resin based on phenol, 37% aqueous formdehyde, dicyandiamide, sodium hydroxide, silane "A-1100" and boric acid is prepared as follows.

A reactor equipped with a stirrer, a reflux condenser and a heating apparatus is charged with 100 parts by weight of phenol, 340 parts by weight of 3,58626 parts of 37% aqueous formaldehyde solution and 3.7 parts by weight of sodium hydroxide. The pH of the solution in the reactor should be between 8.5 and 9.0.

The process is carried out at a temperature of 70 ° C until the concentration of free formaldehyde in the reaction medium falls below 12% by weight.

The mixture is cooled to a temperature between 40 and 50 ° C and the medium is neutralized with boric acid to pH = 7.5 to 8.0. 40 parts by weight of dicyandiamide are then added to the reactor and the mixture is heated to 60-70 ° C. Immediately after the dissolution of the dicyandiamide, the resulting modified resoliphenol-formaldehyde resin is cooled to 40 ° C and 0.001 to 2% by weight of silane "A-1100" is added.

One disadvantage of the above heat insulating agent is the complexity of the synthesis and the high cost of the water-resistant additive, namely aminopropyltriethoxysilane (A-1100) used in the binder. In addition, it is known that silane "A-1100" is an effective water-resistant agent only for mineral fibers with a high silicate modulus (M_ = 2.28-2.4).

It is an object of the present invention to obviate the above-mentioned disadvantages.

The main object of the invention is to use a water-resistant additive readily available and easy to prepare in the binder, which provides a reduction in moisture absorption and an increase in the moisture resistance of the thermal insulation material.

This object is achieved by a thermal insulating agent containing 85 to 98 parts by weight of mineral wool and 15 to 2 parts by weight of a binder applied to this wool, which is a modified resole-phenol-formaldehyde resin based on phenol, formaldehyde, sodium hydroxide, water-resistant hydroxide, additive, as well as urea or dicyandiamide or melamine, according to the invention contains as water-resistant additive a single alkyl resorcinol having 2 to 8 side chain carbon atoms or a mixture of alkyl esorsinols, the ratio of phenol, formaldehyde or sodium amide amide is as follows (parts by weight): 4,58626 phenol - 1 formaldehyde - 0.74 - 0.96 sodium hydroxide - 0.03 - 0.05 alkylresorcinol with 2-8 side chain carbon towers, or a mixture of alkyl resorcinols - 0.075-0.045 urea, or dicyandiamide or melamine - 0.15 to 0.35

The proposed invention is implemented as follows.

A reactor equipped with a mechanical stirrer, a thermometer and a reflux condenser is charged with 100 parts by weight of phenol, 3-5 parts by weight of sodium hydroxide (as a 20% aqueous solution) and 74 to 96 parts by weight of formaldehyde (46 to 70 ° C). 37% as an aqueous solution).

The polycondensation is carried out with constant stirring at a temperature of 50-60 ° C for 6-10 hours. 7.5 to 45 parts by weight of a mixture of alkyl resorcinols or a single alkyl resorcinol having 2 to 8 side chain carbon atoms are then charged to the reactor, and the polycondensation is continued at 50 to 70 ° C for 1.5 to 4 hours. Thereafter, 15 to 35 parts by weight of urea or dicyandiamide or melamine are introduced into the reactor and the polycondensation is continued for 0.5 to 2.5 hours at a temperature of 50 to 70 ° C.

To obtain a heat insulating agent, the obtained aqueous solution of a binder which is a modified resolifenol-formaldehyde resin is applied to the mineral wool by spraying into the fiber standing chamber or impregnating the mineral fibers, and then heat treating the heat insulating agent. The choice of the ratio between the starting components to obtain the binder according to the invention guarantees, after three months of storage, the viscosity of the binder up to 150 es and sufficient miscibility with water (1: 5). In addition, minimum levels of free phenol (up to 2.0% by weight), formaldehyde (up to 2.5% by weight and alkali (up to 0.6% by weight)) are achieved due to the introduction of a water-resistant additive into the binder combination. , namely by introducing an alkyl resorcinol having 2 to 8 side chain carbon atoms or a mixture of alkyl resorcinols, moisture does not penetrate through the contact surface between the cured binder and the mineral fiber, which are components of the heat insulating agent.

5,58626

Containing the proposed binder! the adhesion of the thermal insulation material is 15% higher than that of a thermal insulation material with a binder of the same composition but no alkyl resorcinol, reduced mass water absorption (40.40% instead of 350-400%) and increased moisture resistance (residual adhesion after 72 hours of storage); after a humid atmosphere is 1.5 to 2 times higher.

In addition, the proposed substance, compared to thermal insulation materials manufactured by well-known companies such as Rockwool Ab, Sweden, Ahlström Oy, Finland, and Jungers Verkstads Ab Sweden, which contain special organosilicone additives in the binder combination, allows them to be replaced by simpler ones. such as alkyl resorcinol or a mixture of alkyl resorcinols. The optimal water absorption of the above-mentioned companies for thermal insulation compositions is 30-45%.

The moisture resistance of the proposed and prior art binders incorporated in the thermal insulation materials is as follows in the tables.

1 2 3 4

Modified resoliphenol-formaldehyde resin based on phenol, formaldehyde, sodium hydroxide, urea, used in the following proportions (parts by weight): phenol - 100 sodium hydroxide - 22.5 urea -17.9 6.4 2.2 34.3

The same composition as above, wherein the binder also contains in the combination 22.8 parts by weight of a water-resistant additive - a mixture of shale alkyl resorcinols having the following composition by weight: resorcinol - 3,5-methylresorcinol - 45 5-ethylresorcinol - 10 4,5-Dimethylresorcinol - 9 2,5-Dimethylresorcinol - 15 Higher homologues of alkylresorcinols - 18 7.3 4.1 56.1 6 58626 1 2 3 4

Same combination as above, except that the water-resistant additive is 20 parts by weight of hexylresorcinol 8.3 5.9 71.1

The same combination as above, except that the water-resistant additive is β-aminopropylethoxysilane in an amount of 2% by weight based on the weight of the resulting resin. 7.7 4.6 59.7 To better understand this invention, the following examples of its practical application for illustrative purposes are given. Example 1

A reactor equipped with a mechanical stirrer, a thermometer and a reflux condenser is charged at a temperature of 55 to 3 ° C * with 100 parts by weight of phenol, 233 parts by weight of a 37% aqueous solution of formaldehyde and 22.5 parts by weight of 20% aqueous sodium hydroxide solution. The polycondensation is carried out at the same temperature for 8 hours. A water-resistant additive, namely 22.8 parts by weight of a mixture of alkyl resorcinols, is then introduced into the reactor and the polycondensation is continued at 60 + 3 ° C for 2.5 hours. Finally, 17.9 parts by weight of urea are introduced into the reactor and the mixture is allowed to polycondensed at 65 ° C for 1.5 hours.

To obtain a heat insulating agent, an aqueous solution (1: 5 dilution ratio) of the above-obtained binder which is a modified resole formaldehyde resin is applied to mineral wool by any known method and then heat-treated at 140-200 ° C for 30 minutes.

As the mixture of alkyl resorcinols, a heat treatment product of oil shale is used, which is a mixture of different alkyl derivatives of resorcinols having the following average composition (parts by weight): resorcinol - 3 5-methylesorcinol - 45 5-ethylresorcinol - 10 4,5-dimethylesorcinol - 9 2, 5pdimethylsorcinol - 15 higher horologs of alkyl resorcinols - 18.

7,58626

Refractive index of the resulting binder ηβ = 1.465 at 20 ° C.

The obtained thermal insulation material has the following properties: adhesion - 6.1 kg of mass water absorption - 37.4% and contains 3.3 parts by weight of binder.

Adhesion is determined by measuring the force required to pull the yarn from a glass fiber fabric impregnated and cured with a binder incorporated into a thermal insulation material (cf. RPUchin-gens and H.Sh.Girzonas, "Determination of Adhesion of Phenol-Formaldehyde Resins to Glass Fibers". of the Heat Insulation Research Institute, Vilnius (Vilnius, No. 6,1972). Example 2

The process is carried out in the same manner as described in Example 1, except that 200 parts by weight of a 37% aqueous solution of formaldehyde and 7.5 parts by weight of the alkyl resorcinol mixture described in Example 1 are charged to the reactor as a water-resistant additive.

Refractive index of the resulting binder ηβ = 1.467 at 20 ° C.

To obtain a heat insulating agent, a binder modified modified resolphenol-formaldehyde resin in the form of an aqueous solution (dilution ratio 1: 5) is applied to mineral wool by any known method, and the resulting heat insulating agent is heat-treated at 140-200 ° C for 30 minutes.

The obtained thermal insulation material has the following properties: adhesion - 6.8 kg mass water absorption - 51.5% and contains 3.7 parts by weight of binder.

Example 3

The binder is synthesized as in Example 1, but 260 parts by weight of a 37% by weight aqueous solution of formaldehyde and 45 parts by weight of an alkyl resorcinol mixture having the composition described in Example 1 are introduced into the reactor as a water-resistant additive. The resulting binder, which is a modified resolifenol formaldehyde resin, has a refractive index nQ = 1.465 at 20 ° C.

To obtain the heat insulating agent, the binder is applied, in the form of an aqueous solution (dilution ratio 1: 5), to the mineral wool by any known method, and the heat insulating agent is subjected to heat treatment at 8,586,26 at 140-200 ° C for 30 minutes. The thermal insulation material has the following properties: adhesion - 8.1 kg mass water absorption - 38% and contains 2.0 parts by weight of binder.

Example 4

The binder is synthesized as in Example 1, but 20 parts by weight of 4-hexylresorcinol are introduced into the reactor as a water-resistant additive.

The resulting binder, a modified resoliphenol-formaldehyde resin, has a refractive index ηβ = 1.466 at 20 ° C.

To obtain a heat insulating agent, the obtained binder is applied, in the form of an aqueous solution (dilution ratio 1: 5) to mineral wool by some known method, and the obtained heat insulating agent is subjected to a heat treatment at 140-200 ° C for 30 minutes. The thermal insulation material has the following properties: adhesion - 8.3 kg mass water absorption - 34% and contains 3.8 parts by weight of binder.

Example 5

The binder is synthesized as in Example 1, but 35 parts by weight of 5-ethylresorcinol are introduced into the reactor as a water-resistant additive.

The resulting binder, which is a modified resolifenol-formaldehyde resin, has a refractive index ηβ = 1.465 at 20 ° C.

The binder obtained to obtain the heat insulating agent is applied in the form of an aqueous solution (dilution ratio 1: 5) to the mineral wool by some known method, then the obtained heat insulating agent is subjected to a heat treatment at 140-200 ° C for 30 minutes. The thermal insulation material has the following properties: adhesion - 7.8 kg mass water absorption - 40% and contains 4.2 parts by weight of binder.

Example 6

The binder is synthesized as in Example 1, except that parts by weight of urea are used.

9,58626

The resulting binder, which is a modified resolifenol-formaldehyde resin, has a refractive index ηβ = 1.470 at 20 ° C.

The binder obtained to obtain the heat insulating agent, in the form of an aqueous solution (dilution ratio 1: 5), is applied to the mineral wool by any known method, and the obtained heat insulating agent is subjected to a heat treatment at 140-200 ° C for 30 minutes. The thermal insulation material has the following properties: adhesion - 7.3 kg mass water absorption - 50% and it contains 15 parts by weight of binder.

Example 7

The synthesis is carried out in the same manner as described in Example 1, but instead of urea, 25 parts by weight of melamine are introduced into the reactor.

The resulting binder, which is a modified resolifenol-formaldehyde resin, has a refractive index nQ = 1.469 at 20 ° C.

The binder obtained to obtain the heat insulating agent, in the form of an aqueous solution (dilution ratio 1: 5), is applied to the mineral wool and the obtained heat insulating agent is subjected to a heat treatment at 140-200 ° C for 30 minutes.

The thermal insulation material has the following properties: adhesion - 6.9 kg mass water absorption - 42% and contains 5.9 parts by weight of binder.

Example 8

The synthesis is carried out as in Example 1, but instead of urea, 25 parts by weight of dicyandiamide are introduced into the reactor.

The resulting binder, a modified resolifenol-formaldehyde resin, has a refractive index nD = 1.468 at 20 ° C.

The binder formed to obtain the heat insulating agent, in the form of an aqueous solution (dilution ratio 1: 5), is applied to the mineral wool and the resulting heat insulating agent is subjected to a heat treatment at 140-200 ° C for 30 minutes.

The thermal insulation material has the following properties: adhesion - 6.8 kg mass water absorption - 39% and contains 5.1 parts by weight of binder.

10 58626

Example 9

A reactor equipped with a mechanical stirrer, a thermometer and a reflux condenser is charged at 50 to 3 ° C with 100 parts by weight of phenol, 200 parts by weight of a 37% aqueous solution of formaldehyde and 15 parts by weight of a 20% aqueous solution of sodium hydroxide. The polycondensation is carried out at the same temperature for 6 hours. A waterproofing additive, namely 7.5 parts by weight of a mixture of alkyl resorcinols, the composition of which is described in Example 1, is then introduced into the reactor. The polycondensation is carried out at a temperature of 55-3 ° C for 2.5 hours. Finally, 15 parts by weight of urea are introduced into the reactor and the mixture is made to polycondensate at 55-3 ° C for 0.5 hours.

An aqueous solution (1: 5 dilution ratio) of the resulting binder, a modified resolifenol-formaldehyde resin, to obtain a heat insulating agent is applied to mineral wool by a known method, and the resulting heat insulating agent is subjected to a heat treatment at 140 to 200 ° C for 30 minutes.

The resulting binder, a modified resolifenol-formaldehyde resin, has a refractive index nD = 1.466 at 20 ° C.

The obtained thermal insulation material has the following properties: adhesion - 6.4 kg mass water absorption - 50% and contains 5 parts by weight of binder.

Example 10

A reactor equipped with a mechanical stirrer, a thermometer and a reflux condenser is charged at a temperature of 65 to 3 ° C with 100 parts by weight of phenol, 260 parts by weight of a 37% aqueous solution of formaldehyde and 25 parts by weight of a 20% aqueous solution of sodium hydroxide. .

The polycondensation is carried out at the same temperature for 10 hours. The reactor is then charged with a waterproofing additive, i.e., 45 parts by weight of a mixture of alkyl resorcinols having the composition described in Example 1. The polycondensation is carried out at a temperature of 65 to 3 ° C for 4 hours. Finally, 35 parts by weight of urea are introduced into the reactor and the mixture is brought to polycondensation at a temperature of 54 to 3 ° C for 2.5 hours.

An aqueous solution (1: 5 dilution ratio) of the resulting binder, a modified resoliphenol-formaldehyde resin, is applied to the mineral wool by a known method, and the resulting heat insulator is heat-treated at 140-200 ° C for 30 minutes.

The refractive index of the modified resolifenol-formaldehyde resin of the resulting binder is nD = 1.469 at 20 ° C.

The obtained thermal insulation material has the following properties: adhesion - 7.5 kg mass water absorption - 45% and contains 15 parts by weight of binder.

Claims (1)

12 5 8 6 2 6 Claim: A thermal insulating agent containing 85 to 98 parts by weight of mineral wool and 15 to 2 parts by weight of a binder applied to this wool, which is a modified resolifenol-formaldehyde resin based on phenol »formaldehyde, sodium hydroxide, water-resistant additive, as well as urea or dicyandiamide or melamine, characterized in that the heat-insulating agent contains as a water-resistant additive a single alkyl resorcinol having 2 to 8 side chain carbon atoms or a mixture of alkyl resorcinol formaldehyde, hydroxide, alkyl resorcinols and also urea or dicyandiamide or melamine is as follows (in parts by weight): phenol - 1 formaldehyde - 0.74 - 0.96 sodium hydroxide - 0.03 - 0.05 alkyl resorcinol in which the number of side atomic atoms is 2- 8, or a mixture of alkyl resorcinols - 0.075 to 0.45 urea or dicyandiamide or melamine - 0.15 to 0.35