阅读说明：本技术 聚醚组合物、以其为原料的聚氨酯硬泡及其制备方法 (Polyether composition, polyurethane rigid foam using polyether composition as raw material and preparation method of polyurethane rigid foam ) 是由 任浩军 李玉博 于 2021-08-02 设计创作，主要内容包括：本发明公开了一种聚醚组合物,其原料包括官能度为6-8,羟值450-600第一聚醚多元醇,官能度为5-6,羟值20-40的第二聚醚多元醇和聚酯多元醇。本发明还公开了一种聚氨酯硬泡,其原料包括上述聚醚组合物和异氰酸酯。本发明还公开了上述聚氨酯硬泡的制备方法。本发明所提供的聚氨酯泡沫由于使用了特定的聚醚多元醇组合,使得最终得到聚氨酯泡沫的不仅具有较高的机械强度,同时具有良好的韧性；本发明制备方法简单便捷,节省工期。(The invention discloses a polyether composition, which comprises raw materials of a first polyether polyol with the functionality of 6-8 and the hydroxyl value of 450-600, a second polyether polyol with the functionality of 5-6 and the hydroxyl value of 20-40 and a polyester polyol. The invention also discloses a polyurethane rigid foam, which comprises the polyether composition and isocyanate as raw materials. The invention also discloses a preparation method of the polyurethane rigid foam. The polyurethane foam provided by the invention uses the specific polyether polyol combination, so that the finally obtained polyurethane foam not only has higher mechanical strength, but also has good toughness; the preparation method is simple and convenient, and the construction period is saved.)

1. A polyether composition is characterized by comprising, in parts by mass,

20-40 parts of first polyether polyol;

20-40 parts of second polyether polyol;

20-40 parts of polyester polyol;

the first polyether polyol has a functionality of 6-8 and a hydroxyl value of 450-600;

the second polyether polyol has a functionality of 5 to 6 and a hydroxyl value of 20 to 40.

2. The polyether composition of claim 1 wherein the polyester polyol has a functionality of 2 and a hydroxyl number of 200-300.

3. The polyether composition according to claim 1 or 2, further comprising 5 to 10 parts by mass of a physical blowing agent, 1.5 to 2 parts by mass of water, 4 to 8 parts by mass of a catalyst, and 5 to 10 parts by mass of a crosslinking agent.

4. The polyether composition of claim 3, wherein the cross-linking agent comprises at least one of glycerol and triethanolamine; and/or the presence of a gas in the gas,

the catalyst is at least one of amine and organic metal catalyst; and/or the presence of a gas in the gas,

the physical blowing agent is pentafluoropropane.

5. The polyether composition according to claim 4, further comprising 0.5 to 2 parts by mass of a foam stabilizer and/or 10 to 40 parts by mass of a flame retardant.

6. The polyether composition of claim 5 wherein the foam stabilizer is a polydimethylsiloxane-alkylene oxide copolymer; and/or the presence of a gas in the gas,

the flame retardant is at least one of triethyl phosphate, tri (chloroisopropyl) phosphate and tri (chloroethyl) phosphate.

7. A rigid polyurethane foam comprising the polyether composition of any one of claims 1 to 6 and an isocyanate in a weight ratio of 1: 1.

8. The rigid polyurethane foam according to claim 7, wherein the isocyanate is polyphenyl polymethylene isocyanate and the NCO mass fraction is 30 to 32%.

9. The preparation method of the rigid polyurethane foam is characterized by comprising the following steps: the polyurethane rigid foam of claim 7 or 8 is prepared by mixing uniformly, foaming and forming.

Technical Field

The invention relates to the technical field of polyurethane rigid foam synthesis, in particular to a polyether composition, a polyurethane rigid foam using the polyether composition as a raw material and a preparation method of the polyurethane rigid foam.

Background

With the high-speed development of economy, the demand of national sports and entertainment is strong, common people in China have more and more opportunities of carrying out sports stadium competition and entertainment, and China gradually changes from a large sports country to a strong sports country. In order to meet the development of sports career in China and the requirements of the masses on high-level and high-quality stadiums, building enterprises in China gradually pay attention to the use of advanced energy-saving and environment-friendly materials in the construction process of the stadiums under the call of national policies and social requirements. Indoor ice and snow venues are particularly prominent in energy consumption due to environmental particularity, and energy-saving designs are applied to more and more designs in order to reduce energy consumption.

The polyurethane material has been widely applied to heat preservation in various fields such as household appliances, buildings, fresh transportation and the like due to excellent heat preservation performance, mechanical property and chemical resistance. Polyurethane spraying foaming can directly combine with wall ground heated board, and the construction speed is fast, and the wholeness is good, can improve the thermal insulation performance of building greatly. However, the prior art does not have the polyurethane rigid foam specially applied to the snow road, because the strength of the high-strength polyurethane rigid foam which is conventionally used for the ground of a refrigeration house still can not reach the snow road load of more than 650kg/m²And the toughness of the composite material can not meet the requirement of snow road pavement.

Disclosure of Invention

Therefore, the invention aims to solve the technical problem that the existing rigid polyurethane foam cannot meet the requirements on snow-road strength and toughness, and further provides a polyether composition, a rigid polyurethane foam using the polyether composition as a raw material and a preparation method of the rigid polyurethane foam.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the invention provides a polyether composition which comprises the following components in parts by weight,

20-40 parts of first polyether polyol;

20-40 parts of second polyether polyol;

20-40 parts of polyester polyol;

the first polyether polyol has a functionality of 6-8 and a hydroxyl value of 450-600;

the second polyether polyol has a functionality of 5 to 6 and a hydroxyl value of 20 to 40.

Further, the polyester polyol has a functionality of 2 and a hydroxyl number of 200-300.

Further comprises 5-10 parts by mass of a physical foaming agent, 1.5-2 parts by mass of water, 4-8 parts by mass of a catalyst and 5-10 parts by mass of a crosslinking agent.

Preferably, the cross-linking agent comprises at least one of glycerol and triethanolamine; and/or the presence of a gas in the gas,

the catalyst is at least one of an amine catalyst comprising at least one of bis (dimethylaminoethyl) ether, triethylenediamine, tris (dimethylaminopropyl) hexahydrotriazine, and an organometallic catalyst comprising at least one of potassium octoate and dibutyltin dilaurate; and/or the presence of a gas in the gas,

the physical blowing agent is pentafluoropropane.

Further, 0.5-2 parts by mass of foam stabilizer and/or 10-40 parts by mass of flame retardant are also included.

Preferably, the foam stabilizer is a polydimethylsiloxane-oxyalkylene copolymer; and/or the presence of a gas in the gas,

the flame retardant is at least one of triethyl phosphate, tri (chloroisopropyl) phosphate and tri (chloroethyl) phosphate.

Mixing the above raw materials thoroughly to obtain polyether composition, wherein the mixing time is 0.5-1h, and the mixing temperature is 15-20 deg.C

The invention also provides a polyurethane rigid foam, which comprises the polyether composition and isocyanate according to the parts by weight, wherein the weight ratio of the polyether composition to the isocyanate is 1:1, and the polyether composition and polyurethane are independently stored.

Further, the isocyanate is polyphenyl polymethylene isocyanate, and the NCO mass fraction (i.e., the mass fraction of isocyanate groups in the isocyanate) is 30-32%.

The invention also provides a preparation method of the polyurethane rigid foam, which comprises the following steps: the polyurethane rigid foam of claim 7 or 8 is prepared by mixing uniformly, foaming and forming.

Compared with the prior art, the invention has the following beneficial effects:

1. the polyether composition provided by the invention limits the use of the first polyether polyol with the functionality of 6-8 and the hydroxyl value of 450-600 and the second polyether polyol with the functionality of 5-6 and the hydroxyl value of 20-40, and when the rigid polyurethane foam is prepared subsequently, the first polyether polyol and the rest raw materials are easier to form a cross-linked network, so that the prepared rigid polyurethane foam contains a large amount of cyclic structures, and meanwhile, the second polyether polyol introduces a flexible long-chain structure to complement the first polyether polyol.

2. When the polyurethane rigid foam provided by the invention is used, the contained cyclic structure belongs to a rigid structure and is difficult to rotate in the polyurethane, so that the hardness of the polymer can be increased, and the brittleness can be increased at the same time; the problem can be improved by introducing a flexible long-chain structure into the second polyether polyol, and the elasticity and softness of the material can be improved, so that the finally obtained polyurethane foam not only has higher mechanical strength, but also has good toughness.

3. The preparation method disclosed by the invention has the advantages that the preparation method is only required to be carried out after uniform mixing and foaming molding, the construction mode is simple and convenient, and the construction period is saved; the environment-friendly foaming agent is adopted, ODS substances are not released to destroy the atmosphere, and the foaming agent has a better heat preservation effect and saves energy compared with a full-water foaming system.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The polyether polyols used in the present invention are all produced by the optimized chemical company Limited, wherein:

polyether polyol 4190, functionality 7, hydroxyl number 490

Polyether polyol 6482, functionality 7, hydroxyl number 480

Polyether polyol 8046, functionality 7, hydroxyl number 460

Polyether polyol 6028, functionality 6, hydroxyl number 28

Polyether polyol 8360 functionality 4.5 hydroxyl number 360

Polyether polyol 310 has a functionality of 3 and a hydroxyl number of 160.

The polyester polyols used were all produced by Nanjing Spiral, where:

polyester polyol 3152, functionality 2.2, hydroxyl number 315

2412 polyester polyol with functionality of 2.2 and hydroxyl value of 240

The foam stabilizer used was a polydimethylsiloxane-oxyalkylene copolymer produced by Meiside chemical Co., Ltd, Jiangsu, in the product types of 8860 and M8193.

The used flame retardant is tri (chloroisopropyl) phosphate and tri (chloroethyl) phosphate produced by optimized chemical company Limited, and triethyl phosphate is produced by Jiangsu Chang Yuan chemical company Limited;

the used physical foaming agent pentafluoropropane is HFC-245fa produced by Honeywell company;

the catalysts used were bis (dimethylaminoethyl) ether, triethylenediamine, tris (dimethylaminopropyl) hexahydrotriazine, potassium octoate and dibutyltin dilaurate, which are produced by air chemical.

The isocyanate used was a polyphenyl polymethylene isocyanate of PM200 type manufactured by Vanhua chemical company with NCO parts by mass of 31%.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

Example 1

The embodiment provides a polyether composition, which comprises the following raw materials:

20kg of polyether polyol 4190, 40kg of polyether polyol 6028 and 30kg of polyester polyol 2412, 10kg of glycerol, 2kg of foam stabilizer 8860, 1.7kg of water, 0.5kg of bis (dimethylaminoethyl) ether, 0.7kg of triethylenediamine, 1.5kg of tris (dimethylaminopropyl) hexahydrotriazine, 0.4kg of potassium octanoate, 0.1kg of dibutyltin dilaurate, 30kg of tris (chloroisopropyl) phosphate, 15kg of triethyl phosphate, 6kg of pentafluoropropane.

The preparation method comprises the following steps:

mixing the raw materials, and stirring at 20 ℃ for 0.5h to obtain a polyether composition;

the embodiment also provides a polyurethane rigid foam, which comprises the following raw materials:

156.4kg of the above polyether composition and 156.4kg of isocyanate.

The preparation method comprises the following steps:

and (3) mixing and spraying the polyether composition and isocyanate on the ground of a venue by using a high-pressure sprayer, and foaming and molding to obtain the polyurethane rigid foam.

Example 2

The embodiment provides a polyether composition, which comprises the following raw materials:

30kg of polyether polyol 6482, 30kg of polyether polyol 6028, 35kg of polyester polyol 2412, 5kg of triethanolamine, 2kg of foam stabilizer M8193, 1.8kg of water, 0.4kg of bis (dimethylaminoethyl) ether, 0.7kg of triethylenediamine, 1.2kg of tris (dimethylaminopropyl) hexahydrotriazine, 0.4kg of potassium octanoate, 0.1kg of dibutyltin dilaurate, 30kg of tris (chloroethyl) phosphate, 10kg of triethyl phosphate and 5kg of pentafluoropropane.

The preparation method comprises the following steps:

mixing the raw materials, and stirring at 15 ℃ for 1h to obtain a polyether composition;

the embodiment also provides a polyurethane rigid foam, which comprises the following raw materials:

151.6kg of the above polyether composition and 151.6kg of isocyanate.

The preparation method comprises the following steps:

and (3) mixing and spraying the polyether composition and isocyanate on the ground of a venue by using a high-pressure sprayer, and foaming and molding to obtain the polyurethane rigid foam.

Example 3

The embodiment provides a polyether composition, which comprises the following raw materials:

40kg of polyether polyol 8046, 35kg of polyether polyol 6028, 20kg of polyester polyol 3152, 10kg of glycerol, 2kg of foam stabilizer 8860, 1.5kg of water, 0.7kg of bis (dimethylaminoethyl) ether, 0.4kg of triethylenediamine, 1kg of tris (dimethylaminopropyl) hexahydrotriazine, 0.5kg of potassium octanoate, 0.2kg of dibutyltin dilaurate, 10kg of tris (chloroisopropyl) phosphate, 25kg of tris (chloroethyl) phosphate, 15kg of triethyl phosphate, 7kg of pentafluoropropane.

The preparation method comprises the following steps:

mixing the raw materials, and stirring at 18 ℃ for 0.8h to obtain a polyether composition;

the embodiment also provides a polyurethane rigid foam, which comprises the following raw materials:

168.3kg of the above polyether composition and 168.3kg of isocyanate.

The preparation method comprises the following steps:

and (3) mixing and spraying the polyether composition and isocyanate on the ground of a venue by using a high-pressure sprayer, and foaming and molding to obtain the polyurethane rigid foam.

Comparative example 1

This comparative example provides a polyether composition which differs from example 3 in that polyether polyol 8360 is used instead of polyether polyol 8046, starting from:

40kg of polyether polyol 8360, 35kg of polyether polyol 6028, 20kg of polyester polyol 3152, 10kg of glycerol, 2kg of foam stabilizer 8860, 1.5kg of water, 0.7kg of bis (dimethylaminoethyl) ether, 0.4kg of triethylenediamine, 1kg of tris (dimethylaminopropyl) hexahydrotriazine, 0.5kg of potassium octanoate, 0.2kg of dibutyltin dilaurate, 10kg of tris (chloroisopropyl) phosphate, 25kg of tris (chloroethyl) phosphate, 15kg of triethyl phosphate, 7kg of pentafluoropropane.

The preparation method comprises the following steps:

mixing the raw materials, and stirring at 18 ℃ for 0.8h to obtain a polyether composition;

the comparative example also provides a polyurethane rigid foam, which comprises the following raw materials:

168.3kg of the above polyether composition and 168.3kg of isocyanate.

The preparation method comprises the following steps:

and (3) mixing and spraying the polyether composition and isocyanate on the ground of a venue by using a high-pressure sprayer, and foaming and molding to obtain the polyurethane rigid foam.

Comparative example 2

This comparative example provides a polyether composition which differs from example 2 in that polyether polyol 310 is used in place of polyether polyol 6028 by the following starting materials:

30kg of polyether polyol 6482, 30kg of polyether polyol 310, 35kg of polyester polyol 2412, 5kg of triethanolamine, 2kg of foam stabilizer M8193, 1.8kg of water, 0.4kg of bis (dimethylaminoethyl) ether, 0.7kg of triethylenediamine, 1.2kg of tris (dimethylaminopropyl) hexahydrotriazine, 0.4kg of potassium octoate, 0.1kg of dibutyltin dilaurate, 30kg of tris (chloroethyl) phosphate, 10kg of triethyl phosphate and 5kg of pentafluoropropane.

The preparation method comprises the following steps:

mixing the raw materials, and stirring at 15 ℃ for 1h to obtain a polyether composition;

the embodiment also provides a polyurethane rigid foam, which comprises the following raw materials:

151.6kg of the above polyether composition and 151.6kg of isocyanate.

The preparation method comprises the following steps:

and (3) mixing and spraying the polyether composition and isocyanate on the ground of a venue by using a high-pressure sprayer, and foaming and molding to obtain the polyurethane rigid foam.

Test examples

The polyurethane foams prepared in the examples and comparative examples were tested and the results are shown in Table 1:

TABLE 1 polyurethane foam Performance test results

As shown in the table above, in comparative example 1, polyether polyol 8360 was used instead (functionality 4.5, hydroxyl value 360), which has both functionality and hydroxyl value lower than those of polyether polyol 8046, and which is not able to provide a sufficient rigid cyclic structure and a soft and flexible long chain during the reaction process in the preparation of polyurethane foam, as compared to 8046, and the resulting polyurethane rigid foam has inferior compressive strength; comparative example 2 in addition to example 2, polyether polyol 310 (functionality 3, hydroxyl number 160) was used in place of polyether polyol 6028, which, while being flexible and long-chain, did not have a sufficiently rigid crosslinked network during the reaction, and resulted in polyurethane foams having insufficient compressive strength and flexural strength.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.