Composition for preparing soft polyurethane materials

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to formulations of polyurethane elastoplastics designating for preparing soft polyurethane materials with Shore hardness value 45-55 conditional units. Invention describes the composition comprising 74.8-78.4 wt.-% of urethane pre-polymer based on 1.8 mole of 2,4-toluylene diisocyanate and 1.0 mole of polyethylenebutylene glycoladipinate of molecular mass 2000 Da and liquid hardening agent based on aromatic amine 3,3'-dichloro-4,4'-diaminodiphenylmethane and a mixture of oligoesters - polyethylene glycoladipinate of molecular mass 800 Da and polyethylenebutylene glycoladipinate of molecular mass 2000 Da taken in the mole ratio 0.34; 0.33; 0.33 (up to 100 wt.-%). Polyurethane materials prepared on the basis of such composition show Shore hardness value at the level 45 units, rupture strength limit (at 23°C) at the level 31.2 MPa, relative elongation at rupture 1100%, and they can be exploited at temperature -10°C.

EFFECT: improved and valuable properties of composition.

4 tbl, 5 ex

 

The invention relates to formulations of polyurethane elastomers intended for the manufacture of soft polyurethane materials with low hardness of about 45-55 srvc. unit shore A.

Currently, for the manufacture of a wide range of products, the most commonly used polyurethane elastomer obtained by reacting polimorfnogo prepolymer and curing the mixture on the basis of aromatic amine-3,3'-dichloro-4,4'-diaminodiphenylmethane and polyethyleneglycoladipinate with a molecular mass of 800 in the ratio of 0.2:0,68 accordingly /Patent RU 2078773, IPC C 08 G 18/08 from 18.07.1994 g for the invention "Method of producing polyurethane"/.

Known composition provides high strength properties (ultimate tensile strength 33 MPa, relative deformation at break of 700%) and increased survivability of the reaction mass (50-60 min).

However, it is not resistant to organic solvents and gives high values of hardness.

Closest to the claimed composition in composition and technical nature of a polyurethane composition according to patent RU 2067101, IPC C 08 G 18/32 from 03.03.1993, a method of obtaining a molded urethane elastomers.

In the composition described prepolymer with terminal isocyanate groups on the basis of 2,4-toluylene diisocyanate and hydroxyl-containing compounds (polietilenglikoli is hinata or polyoxyethylene-glycol) liquid hardener based on aromatic diamine 3,3'-dichloro-4,4'-diaminodiphenylmethane in the form of a solution in polyethylene-glycolamine with a molecular mass of 800-1700 in the number and 0.2-0.25 moles per 1 mole of prepolymer.

The composition is resistant to large cyclic loads, however, it has low viability of the reaction mixture (45 min) and reduced operating temperature of polyurethane products. In addition, such materials have a high propensity for crystallization, which leads to a strong increase in the hardness of the material.

The technical problem to be solved in the framework of the present invention is to provide recrystallizes during storage and operation of polyurethane elastomer of low hardness 45-55 c.u shore and increased viability of the reaction mass upon reaching a sufficiently high level of strength and relative deformation at break, as well as extended temperature range of operation of the products obtained, i.e. enhancing their frost resistance.

The solution of the above problem is due to the fact that the composition to obtain a soft polyurethane material comprising a prepolymer with terminal isocyanate groups on the basis of 2,4-toluylene diisocyanate and hydroxyl-containing compounds, and liquid hardener based on aromatic diamine 3,3'-dichloro-4,4'-diaminodiphenylmethane and solvent polyethyleneglycoladipinate with molecular weight of 800, as hydroxyl-containing compounds with the holding oligoether-polyethylenbutylenglycoladiapinate with molecular weight of 2000 (P-B), and as solvent liquid hardener - mixture of oligoesters-polyethyleneglycoladipinate with a molecular mass of 800 (ICP-800) and polyethylenbutylenglycoladiapinate with molecular weight of 2000, in the following ratio between the components of the polyurethane composition, wt.%:

Urethane prepolymer on the basis of 1.8 mol
2,4-toluylene diisocyanate and 1.0 mol polyethylenbutylenglycoladiapinate
mol. mass 200074,8-78,4
Liquid hardener based on aromatic amine
3,3'-dichloro-4,4'-diaminodiphenylmethane and a mixture of oligoesters
polyethyleneglycoladipinate with molecular weight of 800 and
polyethylenbutylenglycoladiapinate with molecular weight of 2000
in a molar ratio of 0.34:0,33:0,33Rest

As part of the inventive polyurethane composition is used, the prepolymer P-BUF on the basis of 1.8 mol of 2,4-toluylene diisocyanate (product C) (TU 113-38-95-90) and 1.0 mol of oligoether polyethylenbutylenglycoladiapinate with molecular weight of 2000 (P-B) (TU 38.103582-85).

As the liquid hardener is used otward the tel Aviv-based aromatic amine 3,3'-dichloro-4,4'-diaminodiphenylmethane (Diamete X) (TU 6-14-980-84), polyethyleneglycoladipinate with a molecular mass of 800 (ICP-800) (TU 38.103287-80), oligoether P-BE taken in a molar ratio of 0.34:0,33:0,33.

Technological process of manufacture of the composition to obtain a soft polyurethane materials consists of the following operations:

synthesis of prepolymer on the basis of 2,4-toluylene diisocyanate and oligoether P-BA with molecular weight of 2000;

- cooking liquid hardener solution Diamete X in a mixture of oligoesters P-BA and ICP-800;

- preparation of the reaction mass;

- pouring the reaction mass into molds for the manufacture of products;

curing the reaction mixture in the form at elevated temperatures;

- removing products from moulds.

Synthesis of the prepolymer is carried out in a closed reactor synthesis at a temperature of 65-70°at atmospheric pressure and operating the mixer.

The process of obtaining liquid hardener is performed in a vacuum mixer. At a temperature of 40-45°loaded With oligoether PDA-800, and then P-BA and mixing. This loads the Diameter X, and the temperature in the mixer is increased to 85-95°C. After some time, turns on the vacuum pump and the components are mixed at a residual pressure in the mixer is not more than 15 mm Hg for 1.5-2 h to dissolve Diamete X.

The mixing of the prepolymer and liquid hardener productivity is camping at a temperature of 60-70° S, after which the reaction mass is poured into molds for curing, preheated to a temperature of 80-90°and covered with antiadhesion.

The curing reaction mass in the forms produced in a heat chamber at a temperature of 80-85°C for 3-4 days.

Novelty and inventive step of the present invention involve structural-chemical modification of the material, excluding the processes of crystallization during storage and operation, which lead to a strong increase in the hardness of the material with a sharp decrease in the strain at break and toughness of polyurethane due to the uneven distribution of microcrystalline regions in the material volume. Suppression of crystallization of the material is carried out using a mixture of polyesters polyethylenbutylenglycoladiapinate with molecular weight of 2000 (P-B) and polyethyleneglycoladipinate with a molecular mass of 800 (ICP-800).

The claimed range of ratios between the components are determined experimentally and are optimal from the point of view of structure formation of the polyurethane matrix, allowing the achievement of high complex physico-mechanical characteristics of the finished material.

The viability of the reaction mass was assessed by the results of the research of its rheological characteristics n is the device RHEOTEST-2 in the temperature range of 25-60° C.

The glass transition temperature of the elastomer was determined on a differential scanning calorimeter DSM-2 under conditions of slow heating of samples with a rate of 0.02 deg/sec

Strength properties were determined according to GOST 270-75, hardness shore a according to GOST 263.

The technical essence of the present invention is illustrated by the following experimental data.

In table. 1 shows the formulation of polyurethane compositions, and in table 2 - characteristics of the reaction mixtures and polyurethane elastomers obtained on their basis, in comparison with the prototype.

From table 1 and 2 shows that the composition to obtain a soft polyurethane materials according to the invention is superior to known, taken as a prototype, in terms of: the viability of the reaction mass, hardiness of material, while providing the desired level of hardness and relatively high values of strength and relative deformation at break, i.e. the invention solves the task.

Low hardness polyurethane elastomers 45-55 used on Soroa and increased survivability of the reaction mass is achieved when the ratio between the components is within the claimed range.

The composition of the liquid hardener and its impact on the viability of the polyurethane compositions and physico-fur the technical properties derived from them elastomers are given in tables 3 and 4.

As follows from the analysis of the results of these tables, the change in the molar ratio between Diameter X and a mixture of polyesters in either direction from the optimum (0,34:0,33:0,33) affects the complex physico-mechanical properties of elastomers, the viability of the reaction mass and hardness of the finished material.

Thus, the claimed composition to obtain a soft polyurethane material allows for achieving a high level of most physico-mechanical properties (tensile strength, relative deformation at break) to obtain non-crystalline during storage and operation elastomer having high viability of the reaction mass and low hardness from 45 to 55 c.u shore A.

Table 1
The components of the compositionThe content of components in the composition
mol. sharewt.%.
The placeholderExamples of specific performance
12345
A prepolymer based on 2,4-colorend the isocyanate and polyethyleneglycoladipinate 1,0-----
The prepolymer on the basis of 1.8 mol of 2,4-toluylene diisocyanate and 1.0 mole polyethylenimine-glycolamine mol. mass 2000-72,7(1,0)74,8(1,0)77,1 (1,0)78,4(1,0)79,7(1,0)
3,3'-dichloro-4,4'-diaminodiphenylmethane0,682,1 (0,34)2,6 (0,34)3,7 (0,34)4,1 (0,34)4,5 (0,34)
Polyethyleneglycoladipinate mol. weight 8000,27,2 (0,33)6,2 (0,33)5,5 (0,33)5,0 (0,33)4,5 (0,33)
Polyethylenbutylenglycoladiapinate mol. mass 2000-18,0(0,33)16,4(0,33)13,7(0,33)12,5 (0,33)11,3(0,33)

Table 2
The viability of the reaction mixtures, physical and mechanical properties of elastomers and the operating temperature of the finished productsExamples of specific performance
the placeholder12345
Inespo the institutional capacity of the reaction mixtures at a temperature of 55° C, min.45>9090858070
Hardness shore a, usled764547525562
Tensile strength at break and the temperature (23±2), °C, MPato 33.82022,526,528,431,2
Elongation at break, and temperature (23±2), °,% 70088690011001020950
The operating temperature of polyurethane products, °+10--10-10-10-

Table 3
The components of the compositionThe content of components in the composition, Moldova
123
The prepolymer on the basis of 1.8 mol of 2,4-toluylene diisocyanate and 1.0 mol of oligoether polyethylenbutylenglycoladiapinate mol. mass 20001,01,01,0
3,3'-dichloro-4,4'-diaminodiphenylmethane,3 0,340,5
Polyethyleneglycoladipinate mol. weight 8000,350,330,25
Polyethylenbutylenglycoladiapinate mol. mass 20000,350,330,25

Table 4
The viability of the reaction mixtures and physico-mechanical properties of elastomersExamples of specific performance
123
The viability of the reaction mixtures at a temperature of 60°S, min,958880
Hardness shore a, usled485464
Tensile strength at break and the temperature (23±2), °C, MPa20,025,629,5
Elongation at break, %9111050980

Composition to obtain a soft polyurethane materials containing prepolymer with terminal isocyanate groups on the basis of 2,4-toluylene diisocyanate and hydroxyl-containing compounds, and liquid hardening agent on the basis of the aroma of the economic diamine 3,3'-dichloro-4,4'-diaminodiphenylmethane and solvent polyethyleneglycoladipinate with molecular weight of 800, characterized in that the composition comprises a hydroxyl-containing compound oligoether-polyethylenbutylenglycoladiapinate with molecular weight of 2000, and the solvent liquid hardener mixture of oligoesters - polyethyleneglycoladipinate with molecular weight of 800 and polyethylenbutylenglycoladiapinate with molecular weight of 2000 in the following ratio, wt.%:

Urethane prepolymer based
1.8 mol of 2,4-toluylene diisocyanate and
1.0 mol polyethylenbutylenglycoladiapinate
with molecular weight of 200074,8-78,4
Liquid hardener based on aromatic
Amin 3,3'-dichloro-4,4'-diaminodiphenylmethane
and a mixture of oligoesters-polyethyleneglycoladipinate
with a molecular weight of 800 and
polyethylenbutylenglycoladiapinate with molecular weight
2000 in a molar ratio of 0.34:0,33:0,33Rest



 

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