CS266511B1 - Composition for the production of cellular masses - Google Patents

Abstract

Composition for the production of lightweight materials intended especially for the furniture and automotive industries, where low values of permanent deformation and higher values of resistance to compression are important, consisting of a mixture of 100 wt. d. of liquid rubber based on polybutadiene, terminated with hydroxyl, carboxyl or amine groups, with an average molecular weight of 1.5.10' to 8.10·3 and with an average number functionality of 1.3 to 3.0, diisocyanate and/or polyisocyanate in a molar ratio of reactive groups of liquid rubber and isocyanate groups of 1:1 to 1:10, and further conventional additives such as e.g. water, stabilizers, catalyst, and possibly low-boiling liquids. The composition may further contain up to 99 wt. d. of polyol and a reinforcing and/or non-reinforcing filler.

Description

The invention relates to a composition for the production of expanded materials.

Currently produced lightweight materials, especially upholstery materials used in the furniture and automotive industries, are almost exclusively based on polyurethanes. The range of polyurethane expanded materials is very wide, from soft upholstery expanded materials to hard expanded materials used, for example, in construction. The properties of polyurethane expanded materials can be modified, in addition to the modification of basic raw materials and the application of various types of inorganic and organic fillers, such as kaolin, mica, metal oxides, glass fibers, wood sawdust, etc. their production prices. Depending on the required properties of the expanded materials and the type of filler, the amount of filler is usually in the range of 20 to 50%. An exception is active fillers, such as carbon black, which are applied in amounts of up to 5%, probably due to their difficult dispersibility in polyurethane starting materials.

Low values of permanent deformation and higher values of resistance to compression are important for the furniture and automotive industries. By adding more carbon black to the polyurethane feedstocks, these values are favorably affected, but on the other hand, due to the uneven cellular structure given by the method of mixing the components, the tensile strength and ductility deteriorate.

It is known from AO 238 296 that the hardness of polyurethane foams can be increased while maintaining other viscoelastic properties when 5 to 50% by weight of the polyol component based on polyester polyols and / or polyether polyols is replaced by telechelic hydroxy-substituted rubber. However, for some applications, the value of the resistance to compression of these foams is still too low. .

These disadvantages are eliminated by the composition for the production of expanded materials in a one-stage or two-stage process by filling and reinforcing the composition in a mold or in another molding device according to the invention.

The essence of the invention lies in the fact that the composition consists of a mixture of 100 wt. d. liquid rubber based on polybutadiene terminated by hydroxyl, carboxyl or amine 3 3 'groups with an average molecular weight of 1.5.10 to 8.10 and with a mean numerical functionality of 1.3 to 3.0 and a diisocyanate and / or polyisocyanate, in a molar ratio of reactive of liquid rubber groups and isocyanate groups 1: 1 to 1:10, and common additives such as water, stabilizer, catalyst and optionally low-boiling liquids. The composition may further comprise up to 99 wt. d. polyols, of the polyester polyol or polyether polyol type, and further reinforcing and / or non-reinforcing fillers. Carbon blacks and silica, for example, can be used as reinforcing fillers in amounts of 5 to 1,500 wt. d. per 100 wt. d. liquid rubber. Non-reinforcing fillers, such as kaolin, chalk, limestone, wood sawdust, polymeric or rubber waste with a particle size of 0.01 to 5 mm, can be added in an amount of 10 to 800 wt. d. per 100 wt. d. liquid rubber.

From the composition for the production of expanded materials in a one-stage or two-stage process according to the invention, integral, block and shaped expanded materials can be produced, which expand the range of expanded polyurethane materials. Particularly expanded materials made from liquid rubbers filled with reinforcing fillers by the process according to the invention have properties which cannot be practically achieved with expanded polyurethanes, even by modifying their basic raw materials. Higher stiffness can be achieved in foamed compositions of liquid rubbers filled with carbon black with a low bulk density and a relatively low content of hard segments of polyisocyanates. The values of resistance to compression are also significantly better, which will have a positive effect on products for the furniture and automotive industries.

The following examples further illustrate the invention.

CS 266 511 Bl

Example 1

The one-step process for the production of unfilled foam is to intensively mix the liquid rubber with the liquid diphenylmethane diisocyanate and the other components listed in Table 1 on a pin stirrer for 10 seconds. in three minutes, the composition is reinforced so that it does not stick.

Table 1

Composition of the mixture liquid polybutadiene rubber terminated hydroxyl groups, MH 2,000 100.0 mass d. 4,4-diphenylmethane diisocyanate 76 mass d. water 4.0 mass d. catalyst (mixture of aminated and organometallic catalyst) 0.24 mass, d stabilizer (polyethersiloxanes) 1.5 mass, d Table 2 Physical-mechanical properties -3 bulk density (kg.m) lightweight matter 30 mass d resistance to compression by 40% (kPa) 35 mass d tensile strength (MPa) 0.15 mass, d ductility% 150 mass, d permanent deformation (compression 50% , 23 ° C, 72 h) (%) - 5.2 mass, d

Example 2

A one-step process for the production of a carbon black-filled expanded mass is prepared by preparing a fine dispersion of carbon black in a mixture of liquid rubber and trifunctional polyol on a dispersing device, which is then intensively mixed with other components on a pin mixer for 10 s and poured into the mold. where it tensions and thickens. The composition of the mixture is given in Table 3.

Table 3

Composition of the mixture liquid terminated polybutadiene rubber

hydroxyl groups MH 2,000 100.0 mass d. polyethertriol, MH 6,000 99.0 mass d. soot 44.0 mass d. 4,4'-diphenylmethane diisocyanate 133.4 mass, d * water 7.2 mass d. stabilizer 1.8 mass d. catalyst 1.64 wt. d

Table 4

Physical-mechanical properties of foamed mass -3 'density (kg.m) tensile strength (MPa) elongation (%) compressive resistance by 40% (kPa)

0.19

180

30.5

CS 266 511 Bl

Example 3

The two-stage process for the production of a carbon black-filled foam is carried out in the first stage by mixing oligobutadiene diol and toluene diisocyanate in a reactor, which react to the prepolymer with constant stirring. The carbon black is then dispersed in the prepolymer on a dispersing device. In step 2, the carbon black prepolymer, catalyst and stabilizer are mixed in a mixing chamber. This mixture is poured into a mold where it expands.

Table 5

Composition of the mixture

oligobutadienediol (MH 2,000) carbon black ISAF toluene diisocyanate water stabilizer catalyst 100.0 wt. d. 15.0 wt. d. 30.7 wt. d. 0.2 wt. d. 0.2 wt. d. 1.1 wt. d. Table 6 Physical-mechanical properties of foam bulk density (kg.m 31.5 resistance to compression (kPa) 7.2 tensile strength (MPa) 0.7 ductility (%) 200 permanent deformation (%) 4.1 Example 4 The one-step method of production of expanded material takes place tal · that all the ingredients are mixed the mixture and the composition are poured into a mold preheated to 40 ° C. Foaming and vulcanization in progress · Eat at 50 ° C for about 1 hour, then lighten the product at ambient temperature. Table 7. allows to freely vulcanize at Composition of the mixture carb-terminated polybutadiene (LEN x USSR), MH 3,250, f = 2.7 100 wt. d. toluene diisocyanate 14.4 wt. d. stabilizer 0.5 wt. d. butanediol 3.7 wt. d. triethylenediamine 0.1 wt. d. tin octoate 0.4 wt. d. N-ethylene morpholine Table 8 0.4 wt. d. Physical-mechanical properties of foam bulk density (kg.m) 70 tensile strength (MPa) 0.13 ductility (%) 230 resistance to compression (kPa) 95

CS 266 511 Bl

Example 5

The two-step process for the production of a foam is mixed in step 1 with amine-terminated polybutadiene acrylonitrile and toluene diisocyanate and the mixture is heated to 50 DEG C. under an inert atmosphere with stirring. The preparation time of the prepolymer is 20 minutes. In step 2, butanediol, stabilizer, water, catalysts are added with thorough stirring and the mixture is poured into a mold. Foaming and vulcanization take about 1 hour, then the product is allowed to vulcanize freely.

Table 9

Composition of the mixture

amine-terminated polybutadiene acrylonitrile, MH 3,400, f - 1.85 (Goodrich USA, Hycar ATBN) 100 mass d. toluene diisocyanate 20.4 mass d. butanediol 1.0 mass d. stabilizer 0.5 mass d. ^H 2 ° 1.2 mass d. triethylenediamine 0.05 > mass . d. tin octoate 0.05 । mass . d.

Table 10 • Physical-mechanical properties of the foam

bulk density (kg.m ³ ), 75 tensile strength (MPa) 0.18 ductility (%) 180 resistance to compression (kPa) 120

Example 6

The two-stage process for the production of expanded material is carried out by mixing oligobutadiene diol and toluene isocyanate in the first stage in a reactor, which are then reacted to form a prepolymer with stirring. In step 2, the prepolymer and other components are mixed and the mixture is poured into a mold.

Table 11

Composition of a mixture of oligodiene diisocyanate based on oligodiene diol MH 5 200 and 2,4-toluene diisocyanate, concentration NCO ~ = 5,05.10 ^-4 mol / 9 diphenylmethane diisocyanate butanediol polysiloxane surfactant dibutyltin laurate triethylenediamine water

100 wt. d.

2.5 wt. d.

1.22 wt. d.

0.5 wt. d.

0.35 wt. d.

0.25 wt. d.

3.0 wt. d.

Physico-mechanical properties of foamed mass density (kg / m) 160 resistance to compression (kPa) 60

Example 7

The one-step process of production of expanded material takes place in such a way that all components are mixed,

CS 266 511 B1 to form a foam composition which is then sulfurized in the mold at 50 ° C.

Table 12

Composition of the mixture

oligobutadienediol (MH = 4,500, OH concentration ^- = 6.62.10 ^-4 g / mol) 100 wt. d. toluene diisocyanate 18.6 wt. d. diphenylmethane diisocyanate 28.9 wt. d. triethanolamine 4.2 wt. d. triethylenediamine 0.25 wt. d water 2.0 wt. d. polysiloxane surfactant 1.0 wt. d. Physical-mechanical properties 3 density (kg / m) 60 resistance to compression (kPa) 45

Example 8

From the individual components of the mixture listed in Table 17, a foamed mass was prepared in a one-step manner.

Table 13

Composition of the mixture

polybutadienediol (MH 2,000) 100 mass ♦ d polyester triol (MH 6,000) 80.0 mass d 2,6-toluene diisocyanate · 64.4 mass d water 4.0 mass d stabilizer 1.2 mass d mixture of accelerators (amine and organometallic) '0.8 mass, d Physical-mechanical properties of expanded material 3 density (kg / m) 60 tensile strength (MPa) 0.3 resistance to compression (kPa) 51 Example 9 A blended mass was prepared by mixing the components of the mixture soot. Table 14 Composition of the mixture polybutadienediol (MH 2,000) 100 mass d polyester triol (MH 6,000) 60.0 mass d soot 20.0 mass, d 2,6-toluene diisocyanate 61.3 mass d water 5.0 mass, d stabilizer 0.5 mass, d mixture of accelerators (amine and organometallic) 0.8 mass, d Physical-mechanical properties of expanded material 3 density (kg / m) 40 tensile strength (MPa) 0.2 resistance to compression (kPa) 40

CS 266 511 Bl 7

Claims (3)

OBJECT OF THE INVENTION A composition for the production of expanded materials in a one-stage or two-stage process by foaming and reinforcing the composition in a mold or in another molding device, characterized in that it consists of a mixture of 100 wt. d. Medium-weight hydroxyl, carboxyl or amine-terminated liquid rubber based on polybutadiene 3 3 1.5.10 to 8.10 and with a mean number functionality of 1.3 to 3.0, and a diisocyanate and / or polyisocyanate, in a molar ratio of reactive groups of liquid rubber and isocyanate groups of 1: 1 to 1:10, and common additives such as water, stabilizer, catalyst and optionally low boiling liquids. 2. The composition according to item 1, characterized in that it additionally contains polyester polyols and / or polyether polyols in an amount of up to 99 wt. d. 3. The composition according to item 1, characterized in that it additionally contains reinforcing fillers, e.g. carbon black, silica, in an amount of 5 to 1,500 wt. d. and / or non-reinforcing fillers such as kaolin, chalk, limestone, wood sawdust, polymeric or rubber waste with a particle size of 0.01 to 5 mm, in an amount of 10 to 800 wt. d.