KR101446231B1 - Auto-crusting microp0rous elastomer composition for use in polyurethane foam-filled tire - Google Patents

Abstract

The present invention relates to an integral microporous elastomer composition for use in polyurethane foam tires. Wherein the composition comprises an A component and a B component, wherein the A component comprises a polyester polyol, a polymer polyol, a crosslinking agent and / or a chain extender, a foam stabilizer, a catalyst, and a foaming agent; The component B is an alcohol modified isocyanate, the mass content of -NCO is 18.0 to 20.0%; And a mixing mass ratio of the A component to the B component is 100: 70 to 100. Since the microporous elastomer material made of the composite material has excellent mechanical properties, it is possible to replace the conventional microporous polyurethane elastomer tire produced by using the conventional polyester type shoe sole solution.

Description

TECHNICAL FIELD [0001] The present invention relates to an integral microporous elastomer composition for use in polyurethane foam tires. BACKGROUND OF THE INVENTION < RTI ID = 0.0 >

The present invention relates to a polyurethane elastomer, and more particularly, to a microporous polyurethane elastomer composition for use in a polyurethane foam tire.

The integral microporous polyurethane elastomer is a polyurethane foam elastomer material that forms the coating and the foam core once during the foaming process. It is a new material that mediates foam and elastomer. It has high strength and high toughness because it has both excellent mechanical properties of elastomer and foam material. Therefore, it is light in weight, stable in transmission of compressive stress and excellent in oil resistance, water resistance and fatigue resistance It has advantages. Here, the excellent shock absorbing and buffering action is widely used for parts of a soft property of an automobile such as a tire in place of a conventional rubber material.

In the production of conventional polyurethane foam tires, most of the B material employs a polyester type quasi-polymer, which is a polyurethane shoe sole stock solution which is commonly available on the market. The microporous elastomeric material produced using the polyester type B material has excellent mechanical properties and the foam material has high hardness and good elasticity. However, since the molecular structure of the polymer has a large number of polar ester groups, when the alternating stress acts, the internal heat of the material increases, and a large amount of heat accumulates, so that it can be easily rinsed. Therefore, low-temperature resistance and dynamic mechanical properties of polyester-type polyurethane foam tires are relatively poor. In addition, the ester groups in the polyester polyol are easily hydrolyzed, so that the molecular chain is easily broken or decomposed under hot and humid conditions. As a result, the polyester type microporous elastomer material is poor in hydrolysis resistance and resistance to fungal infection. The polyurethane-based elastomer produced by adopting the polyester-type similar quasi-polymer can effectively solve the above problems. However, since the microporous polyurethane elastomer material prepared by using the general polyester type similar quasi-polymer has too little mechanical properties, the hardness of the epidermis is too low under the same density condition to satisfy the surface hardness of the polyurethane foam tire and the mechanical property standard Hard.

Many prior art patents disclose that the microporous elastomers prepared using the new low unsaturation polyester polyols have relatively good performance. For example, there is a polyurethane microemulsion elastomer used in shoe soles and shoe soles mentioned in Chinese patent CN1341132A, and a polyurethane microemulsion elastomer manufactured in China patent CN1320131A is used for automobile armrests, automobile handles, shoe soles and shoe soles . The Chinese patent CN1986582A relates to a method for improving the mechanical properties of a pulley ester type polyurethane microparticulate elastomer, but the microstructured elastomeric material referred to in the above patent is used exclusively in polyurethane shoe soles or shoe insole materials, It can not be used for the production of foam tires.

The Chinese patent CN101857670A has relatively good mechanical properties as a method of using polycarbonate polyol made from carbon dioxide and epoxides for the preparation of microporous elastomers but the patent is also only applicable to the manufacture of polyurethane shoe insole. Literature data on polyester-type microporous elastomer compositions that can be used for polyurethane tires are hard to find.

The present invention relates to a polyester-type microporous elastomer composition for use in polyurethane foam tires, wherein the polyurethane foam tire of the composition has excellent mechanical properties, good elasticity, relatively high hardness of the epidermis, It has degradability and resistance to fungal infection.

The present invention relates to an integral microporous elastomer composition of a polyurethane foam tire, comprising an A component and a B component. From here,

(1) The component A is prepared by mixing a polyester polyol, a polymer polyol, a crosslinking agent and / or a chain extender, a foam stabilizer, a catalyst and a foaming agent, and calculating the total weight of the polyester polyol and the polymer polyol as 100 parts by weight , The polyester polyol is 60 to 90 parts by weight, the polymer polyol is 10 to 40 parts by weight, and the weight ratio of the other components to the total weight of the polyester polyol and the polymer polyol is:

The crosslinking agent and / or the chain extender is 10 to 25 parts by weight, the foam stabilizer is 0.2 to 2.5 parts by weight, the catalyst is 0.03 to 1.0 part by weight, and the blowing agent is 0.01 to 10 parts by weight.

(2) The component B is an alcohol-modified isocyanate, wherein the mass content of -NCO is 18.0 to 20.0%, and the weight percentage of the raw material component is:

The polyester polyol is 20 to 40%, the alcohol is 0 to 10%, and the isocyanate is 50 to 70%.

(3) The A component and the B component are mixed at a weight ratio of 100: 70-100 to prepare a polyurethane foam tire.

Here, a preferred technique is as follows.

In the component A, the polyester polyol is a low unsaturation polyester polyol having a high primary hydroxyl group content, and has a number average molecular weight of 5,000 to 8,000, a functionality of 2 to 3, and a primary hydroxyl group content ≥ 65 wt%, and an unsaturation degree? 0.008 meq / g.

In the component A, preferably, the polymer polyol is a styrene-acrylonitrile graft modified polyester polyol, and is selected from the group consisting of POP36 / 28, POP93 / 28, POP40 (commercially available).

In the component A, preferably, the cross-linking agent is one or a mixture of one or more of glycerol, trimethylol propane, pentaerythritol, triethanolamine and diethanolamine. The chain extender may be selected from the group consisting of 3,3-dichloro-4,4-diphenyltoluenediamine, 3,5-dimethylthiotoluenediamine, 3,5-diethyltoluenediamine, ethylene glycol, propylene glycol, Diethylene glycol, dipropylene glycol, and 1,3-pentanediol. Preferably, it is 1,4-butanediol. In the component A, the crosslinking agent and the chain extender can be selected at the same time, and one or more of the above-mentioned materials can be used.

Preferably, in said component A, said foam stabilizer is an organosilicon surfactant and is selected from the group consisting of DC 3043 (commercially available) from Air Products and Chemicals, Inc. or TMG Chemicals Co., 8444 (commercially available).

Preferably, in the component A, the catalyst is an organotin catalyst, a tertiary amine catalyst, a dibutyltin dilaurate, triethylenediamine, bis (2-dimethylaminoethyl) ether, 225). ≪ / RTI > The blowing agent is hydrogenated chlorofluorocarbon (HCFC-141B).

In the component B, the polyester polyol is a polyester polyol having a number average molecular weight of 6000 to 8000, a functionality of 3, an unsaturation degree of 0.008 meq / g and a primary hydroxyl group content of 75% use.

In the component B, the alcohol is one or a mixture of one or more of 1,4-butanediol, 2-methyl-1,3-propylene glycol, diethylene glycol, dipropylene glycol and 1,3-pentane diol. The preferred capacity is 5 to 10% of the B component raw material capacity.

In the component B, the isocyanate is 4,4-diphenylmethane diisocyanate or carbodiimide-modified isocyanate.

It is an advantage of the present invention that the polyurethane foam tires made from the composition of the present invention have excellent mechanical properties, good elasticity and relatively high skin hardness.

The present invention has been specifically described with reference to the following examples.

Example  One:

15 kg of polymer polyol (POP36 / 28, manufactured by Shandong Bluestar), 12 kg of 1,4-butanediol, 7 kg of ethylene glycol, 1 kg of glycerol, 84 kg of organosilicon foam stabilizer 8444 (A-33), 0.18 kg of an organic tin catalyst (T-12) and 12 kg of a foaming agent HCFC-141B were weighed and placed in a reactor, After mixing, remove and keep sealed.

33.45 kg of a polyester polyol (EP-3600, produced by Shandong Blue Star) and 1.76 kg of dipropylene glycol were weighed and placed in a reactor, dehydrated in a vacuum (-0.09 MPa) at 100 to 110 ° C for 1.5 to 2 hours Then, the temperature was lowered to 30 to 50 DEG C, 61.62 kg of 4,4-diphenylmethane diisocyanate (pure MDI) was added, the temperature was slowly raised to 80 to 85 DEG C and the reaction was performed for 1.5 to 2 hours, After the carbodiimide-modified MDI is added and stirred for 0.5 hours, the sample is taken, and the mass content of -NCO is adjusted to 19.8%, the temperature is lowered to 40 ° C, and the sample is taken out and sealed.

When used, the temperature of the component A is maintained at 25 to 30 ° C, the temperature of the component B is maintained at 30 to 40 ° C, the materials A and B are rapidly and homogeneously mixed at a weight ratio of 100:90, Followed by casting to obtain a polyurethane-based elastomer tire.

Example  2:

30 kg of polymer polyol (POP36 / 28, manufactured by Shandong Blue Star), 10 kg of 1,4-butanediol, 7 kg of ethylene glycol, 2 kg of dipropylene glycol, 1 kg of glycerol, 0.2 kg of a foam stabilizer DC3043 (manufactured by Shanghai TMG Co.), 0.3 kg of a tertiary amine (A-33), 0.08 kg of an organic tin catalyst (T-12) and 12 kg of a physical foaming agent HCFC-141B were weighed, ° C, uniformly and thoroughly mixed, then taken out and sealed.

33.67 kg of a polyester polyol (EP-3600, manufactured by Shandong Blue Star) and 2.53 kg of dipropylene glycol were weighed and placed in a reactor, dehydrated in a vacuum (-0.09 MPa) at 100 to 110 ° C for 1.5 to 2 hours After the temperature was lowered to 30 to 50 캜, 60.54 kg of 4,4-diphenylmethane diisocyanate (pure MDI) was added, the temperature was slowly raised to 80 to 85 캜, and the reaction was conducted for 1.5 to 2 hours. Of the carbodiimide-modified MDI is added and stirred for 0.5 hours, the sample is taken, and the mass content of -NCO is adjusted to 19.0%, the temperature is lowered to 40 ° C, and the sample is taken out and stored.

When used, the temperature of the component A is maintained at 25 to 30 ° C, the temperature of the component B is maintained at 30 to 40 ° C, the materials A and B are rapidly and homogeneously mixed at a weight ratio of 100:90, Followed by casting to obtain a polyurethane-based elastomer tire.

Comparative Example  One:

The material A adopts the mixing method of Example 1, and the material B adopts the shoe outsole solution B8090 of Xuchuan Chemical Co., Ltd.

Comparative Example  2:

The material A adopts the mixing method of Example 1, and the material B adopts SUPRASEC 2614 as a raw material for Huntsman shoe outsole.

The following table compares the physical properties of the example and comparative products.

Example 1 Example 1 Example 2 Comparative Example 1 Comparative Example 2 Density / Kg / m ³ 850 500 500 500 500 Shore A hardness 86 72 71 73 65 Tensile strength / MPa 9.53 4.55 4.98 4.26 4.03 Bursting strength / KN / m 39.56 20.65 21.85 16.25 16.56 Elongation /% 240 200 225 150 180

As can be seen from the experimental data in the above table, the microporous elastomer composition prepared according to the present invention is excellent in properties and can be replaced with a polyurethane-biodegradable elastomer tire manufactured from a polyolefin shoe outsole.

Claims (10)

In an integral microporous elastomer composition of a polyurethane foam tire,
And comprises a component A and a component B,
(1) The component A is prepared by mixing a polyester polyol, a polymer polyol, a crosslinking agent and / or a chain extender, a foam stabilizer, a catalyst and a foaming agent, and calculating the total weight of the polyester polyol and the polymer polyol to 100 parts by weight , The polyester polyol is 60 to 90 parts by weight, and the polymer polyol is 10 to 40 parts by weight;
The weight ratio of the other components to the total weight of the polyester polyol and the polymer polyol is:
The crosslinking agent and / or the chain extender is 10 to 25 parts by weight, the foam stabilizer is 0.2 to 2.5 parts by weight, the catalyst is 0.03 to 1.0 part by weight, the foaming agent is 0.01 to 10 parts by weight,
(2) The component B is an alcohol-modified isocyanate, wherein the mass content of -NCO is 18.0 to 20.0% and the weight percentage of the raw material component is:
The polyester polyol is 20 to 40%; The alcohol being one or a mixture of one or more of 1,4-butanediol, 2-methyl-1,3-propylene glycol, diethylene glycol, dipropylene glycol and 1,3-pentanediol; 50 to 70% of said isocyanate;
(3) The integral microporous elastomer composition of a polyurethane foam tire, wherein the component A and the component B are mixed in a weight ratio of 100: 70 to 100, and used in the production of a polyurethane foam tire. The method according to claim 1,
In the component A, the polyester polyol is a low unsaturation polyester polyol having a high primary hydroxyl group content;
A number average molecular weight of 5000 to 8000;
The functionality is 2 to 3;
A primary hydroxyl group content ≥65 wt%; And
And an unsaturation degree? 0.008 meq / g. The method according to claim 1,
Wherein the polymer polyol in the component A is a styrene-acrylonitrile graft modified polyester polyol. ≪ RTI ID = 0.0 > 21. < / RTI > The method according to claim 1,
In the component A, the cross-linking agent is one or a mixture of one or more of glycerol, trimethylol propane, pentaerythritol, triethanolamine and diethanolamine; And
The chain extender may be selected from the group consisting of 3,3-dichloro-4,4-diphenyltoluenediamine, 3,5-dimethylthiotoluenediamine, 3,5-diethyltoluenediamine, ethylene glycol, propylene glycol, Diethylene glycol, dipropylene glycol, and 1,3-pentanediol, or a mixture of one or more of the foregoing. The method according to claim 1,
In the component A,
Wherein the foam stabilizer is an organosilicon surfactant;
Wherein the catalyst is an organotin catalyst or / and a tertiary amine catalyst; And
Wherein the blowing agent is hydrogenated chlorofluorocarbon (HCFC-141B). ≪ RTI ID = 0.0 > 21. < / RTI > 6. The method of claim 5,
Wherein the catalyst is one or more of dibutyltin dilaurate, triethylenediamine, bis (2-dimethylaminoethyl) ether and an equilibrium retardation catalyst. 2. The polyurethane foam tire according to claim 1, The method according to claim 1,
In the component B,
Wherein the polyester polyol has a number average molecular weight of 6000 to 8000;
The functionality is 3;
An unsaturation degree? 0.008 meq / g; And
Wherein a polyester polyol having a primary hydroxyl group content of 75% by weight or more is used as the polyurethane foam. delete The method according to claim 1,
In the component B,
The capacity of the alcohol which is one or a mixture of one or more of the above-mentioned 1,4-butanediol, 2-methyl-1,3-propylene glycol, diethylene glycol, dipropylene glycol and 1,3-pentane diol is 5 to 10% By weight based on the total weight of the tire. The method according to claim 1,
In the component B,
Wherein the isocyanate is 4,4-diphenylmethane diisocyanate or carbodiimide modified isocyanate. ≪ RTI ID = 0.0 > 18. < / RTI >