Polyurethane composition

 

(57) Abstract:

The invention relates to compositions of polyurethane elastomers and can be used in the manufacture of tyres and other rubber products, operating in a wide temperature range of operation in the harsh conditions of alternating loads. Describes polyurethane composition for injection molding of elastomers, including polyetherdiol based on a mixture of polyoxyethyleneglycol, polyethyleneglycoladipinate and diethylene glycol with their molar ratio 0,72-0,595:0,18-0,27:0,1-0,15 accordingly, 2,4-toluylenediisocyanate and 3,3'-dichloro-4,4'-diaminodiphenylmethane. The invention allows to obtain elastomers with high physical-mechanical properties - tensile strength, tear resistance, elongation, hardness 92-95.E. table 2.

The invention relates to compositions of polyurethane elastomers with high physical-mechanical properties - strength, breaking strain, stress at 100% elongation, tear resistance, hardness, low residual deformation, providing a high cyclic stability of products at high sign is of solid tyres, rollers cable cars, etc., operating in a wide temperature range of operation.

Currently for manufacturing solid tyres wheels trams, monorail roads tasked with creating a polyurethane material, operating in the temperature range 45oWith alternating loads, cyclic resistance 108and having the following physico-mechanical characteristics according to GOST 262-93, GOST 263-75, GOST 270-75:

Stress at 100% elongation, MPa - 10-15

Ultimate tensile strength, MPa, Not less than 43

Relative deformation at break,% Not less than 480

Relative residual elongation,% Not more than 10

Tear resistance, kN/m - 100

Hardness shore a, at.E. - 92-95

None of the known polyurethane compositions do not provide complex requirements.

Thus, the known polyurethane composition (patent of the Russian Federation 2155781, IPC C 08 G 18/32, 1998) for the manufacture of products using reaction formation based urethane polimorfnogo of prepolymer on the basis of 2,4-toluylene diisocyanate and oligoastrocytoma with 400 MM (Laprol-402) and liquid hardener solution Diamete-X (3,3'-dichloro-4,4'-diaminodiphenylmethane) polypurine when Molly at break, ultimate tensile strength, but not high hardness shore a (88-92.E.). Information about tear resistance, stress at 100% elongation, relative residual elongation, the operating temperature range in the patent no.

A method of obtaining polyurethane elastomers (RF patent 2067101, IPC C 08 G 18/32, 1993) interaction of the prepolymer with terminal isocyanate groups based on hydroxyl-containing compounds (polyoxyethyleneglycol or polyethyleneglycoladipinate with 800-1700 MM) with liquid hardener - a solution of 3,3'-dichloro-4,4'-diaminodiphenylmethane (0,68-0.7 mole per 1 mole of prepolymer) polyethyleneglycoladipinate with 800-1700 MM, taken in an amount of 0.2-0.25 mole per 1 mole of prepolymer. As the curing agent compositions are polyethyleneglycoladipinate and 3,3'-dichloro-4,4'-diaminodiphenylmethane that leads to the formation of reticulated elastomer containing in the polymer chain link along with urethane and urea groups formed at an additional curing urethane group.

The elastomers obtained in this way are at high relative lengthening of insufficient strength at break (not more than 42,9 MPa), low napta polyurethane composition (patent of the Russian Federation 2130038, IPC 08 G 18/32, 1987), with high physical-mechanical characteristics providing high cyclic stability of products based on it.

The elastomer produced by interaction of polyethyleneglycoladipinate (polyester P-6) with 2,4-diisocyanate, followed by additional processing of the prepolymer 2,4-diisocyanate, butanediol, basic dye triarylmethane and curing 3,3'-dichloro-4,4'-diaminodiphenylmethane. In the patent do not provide specific values of physical and mechanical characteristics, but on the basis of use as the main diol in the synthesis of polyethyleneglycoladipinate, it should be assumed that the stress at 100% elongation of the elastomer is located on the 3rd level of 6-8 MPa. Similar polyurethane elastomers, such as polyurethane SKU-7L, have a stress at 100% elongation 5-7 MPa and operable in the temperature range of 80 plus or minus 25oC.

Closest to the claimed composition to the technical nature and purpose of composition is to obtain a castable polyurethane elastomers (RF patent 2043369 C1 IPC C 08 G 18/32, 1995, bull. 25), intended for the manufacture of molded elastomeric products.

Composition cluen with m m 800 and 3,3'-dichloro-4,4'-diaminodiphenylmethane.

These components are mixed and poured to obtain products in injection form, utverjdayut step at temperatures (805)oWith and (1105)oC.

A disadvantage of the known compositions is that the resulting elastomers have insufficient hardness (up to 79.E.), low tear resistance (up to 70 kN/m), low stress at 100% elongation (to 4.7 MPa), insufficient tensile strength tensile (up to 32 MPa), the cyclic resistance to fracture (10500).

An object of the invention is to improve operational properties of elastomers by creating a polyurethane composition, producing elastomer-based polyoxyethyleneglycol with high mechanical characteristics, requirements for materials for solid tyres and above.

The problem is solved due to the fact that in contrast to the known, the proposed composition in addition to polyoxyethyleneglycol, 2,4-toluylenediisocyanate and 3,3'-dichloro-4,4'-diaminodiphenylmethane contains polyethyleneglycoladipinate and diethylene glycol in the manner prescribed by experimental molar ratio of the non optimal set of characteristics of the elastomer. Thus polyethyleneglycoladipinate is a mixture of polyetherdiols, and 3,3'-dichloro-4,4'-diaminodiphenylmethane acts as a self-curing agent in its own melt, and not in a solution of hydroxyl-containing polyesters.

Found molar ratio meet the following mass ratios of the components of polyurethane compositions, wt.h.:

Polyoxyethyleneglycol - 54,1-66,9

Polyethyleneglycoladipinate - 32,1-44,7

Diethylene glycol - 0,9-1,5

2,4-Toluylenediisocyanate - 28,4 to 31.8

3,3'-Dichloro-4,4'-diaminodiphenylmethane - 15,4-16,6

Novelty and inventive step of the invention lies in the fact that as a result of its implementation achieved a high level of hardness of the elastomer (92-95. E. ), tensile strength (not less than 43 MPa), the relative deformation (480%) tear resistance (not less than 100 kN/m) stress at 100% elongation at the level of 10-15 MPa, which is obvious, as it is impossible to predict in advance that the proposed chemical modification of polyurethane compositions are obtained elastomers, which along with microaggregate hard blocks is formed of a dispersed phase (obviously the reaction product of Diamet-X dietilenglikoluretan when implementing the found ratios of the components of the composition high physical-mechanical characteristics of the elastomer.

The elastomer produced from the inventive polyurethane composition method, the essence of which is that in the reactor was placed a mixture of polyoxyethyleneglycol, polyethyleneglycoladipinate and diethylene glycol, prepared under the given ratios and under stirring and the temperature (555)oTo enter 2,4-toluylenediisocyanate. The reaction mixture is maintained at a temperature (805)oWith intensive stirring for 2-3 hours, cooled to 60oTo add a portion of the melt 3,3'-dichloro-4,4'-diaminodiphenylmethane and mix. The polymer is poured into a mold and put on the cure.

The invention was used components that meet the following technical documentation:

Polyoxyethyleneglycol - polyphonic - TU 6-02-646-81

Polyethyleneglycoladipinate - polyester P-6 - TU 38-103-582-85

Diethylene glycol - GOST 10136-77

2,4-toluylenediisocyanate - product T - TU 113-38-95-90

3,3'-dichloro-4,4'-diaminodiphenylmethane - TU 6-14-980-84

Example 1 (prototype). 100 g (0.1 m) polyoxyethyleneglycol and 34.8 g (0.2 m) of 2,4-toluylene diisocyanate are heated with stirring, the temperature (805)oWith a residual pressure of not more than 20 mm RT. Art. 5 hours and at a temperature (605)o the one with 800 MM and polyoxyethyleneglycol with 1000 MM, taken in a molar ratio of 1:1. The reaction mixture is poured into a mold and utverjdayut speed when temperature: 24 hours at (805)oC and 12 h at (1105)oC.

Example 5. 98 g of polyoxyethyleneglycol MM 980 (HE 3,47%) are mixed at a temperature of (555)oWith a residual pressure of not more than 20 mm RT. Art. from 80.5 g polyethyleneglycoladipinate MM 1880 (HE is 1.81%) and 1.7 g (0,016 m) of diethylene glycol for 30 minutes and injected into the mixture 52,46 g of 2,4-toluylene diisocyanate. The reaction mixture was kept under vigorous stirring, the temperature (805)oC and a relative pressure of not more than 20 mm RT. Art. 2-4 hours until a constant content of NCO-groups, cooled to 60oWith and enter the melt to 36.8 g of 3,3'-dichloro-4,4'-diaminodiphenylmethane. After averaging under stirring for 5 min the reaction mixture is poured into molds. The persistence of a mixture of 30 minutes

Examples 2-4, 6-16. Analogously to example 5 at the ratios of reagents shown in table 1 (examples 2-4, 6-16).

Table 1 shows the formulation of polyurethane compositions, and table 2 - comparative physico-mechanical characteristics of the resulting polyurethane elastomers.

Presented in tables 1, 2 data suggest that the required level of physical and mechanical the positions (PL. 1, 2, examples 6, 7, 10, 13, 16). Deviation of the ratios from the optimum leads to deterioration of certain characteristics (table. 1, 2, examples 2, 3, 4, 5, 8, 9, 11, 12, 14, 15).

As a result of implementation of the invention can obtain a polyurethane elastomer, superior to the prototype (table. 1, 2, example 1) by the complex characteristics and having at a temperature of 20oWITH:

Ultimate tensile strength, MPa - 43,0-50,0

Stress at 100% elongation, MPa - 10-15

Relative deformation at rupture, % - 480-530

Relative residual elongation, %, not more than - 8

Tear resistance, kN/m 100-150

Hardness,.E. - 92-95

Temperature range of operation,oS - 45

Polyurethane elastomer has a cyclic resistance with alternating loads more than 107.

Sources of information

1. RF patent 2155781, IPC C 08 G 18/32, 1998;

2. RF patent 2067101, IPC C 08 G 18/32, 1993;

3. RF patent 2130038, IPC C 08 G 18/32, 1987;

4. RF patent 2043369 C1 IPC C 08 G 18/32, 1995, bull. 25 (prototype).

Polyurethane composition for injection molding of elastomers, including polyetherdiol based polyoxyethyleneglycol and polyethyleneglycoladipinate, 2,4-toluylenediisocyanate and 3,3'-dichloro-4,tetraethyleneglycol and polyethyleneglycoladipinate and additionally diethylene glycol when a molar ratio of 0,72-0,595:0,18-0,27:0,1-0,15 accordingly, in the following ratio of the components of the composition, wt.h.:

Polyoxyethyleneglycol - 54,1-66,9

Polyethyleneglycoladipinate - 32,1-44,7

Diethylene glycol - 0,9-1,5

2,4-Toluylenediisocyanate - 28,4 to 31.8

3,3'-Dichloro-4,4'-diaminodiphenylmethane with 15.4-16.6 g

 

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13 cl, 4 ex

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