阅读说明：本技术 耐高温耐老化聚氨酯材料及其制备方法 (High-temperature-resistant and aging-resistant polyurethane material and preparation method thereof ) 是由 施海云 董家鑫 姚嵩 于 2020-12-30 设计创作，主要内容包括：本发明涉及一种耐高温耐老化聚氨酯材料及其制备方法,主要解决了现有技术中用于汽车聚氨酯材料的耐老化性能差和耐高温性能差的技术问题。本发明通过采用一种耐高温耐老化聚氨酯材料,由组分A和组分B反应制备得到,组分A与组分B的重量份数为100:40～80份,其中组分A以重量份数计包括聚醚多元醇Ⅰ1～30份,聚醚多元醇Ⅱ50～90份,聚合物多元醇0～20份,交联剂1～5份,催化剂0.5～1份,泡沫稳定剂0.5～2份,水1.5～2.5份,抗氧剂0.1～2份；组分B以重量份数计包括异氰酸酯10～30份,改性异氰酸酯70～90份的技术方案较好的解决了该问题。(The invention relates to a high-temperature-resistant and aging-resistant polyurethane material and a preparation method thereof, and mainly solves the technical problems of poor aging resistance and poor high-temperature resistance of the polyurethane material for automobiles in the prior art. The high-temperature-resistant and aging-resistant polyurethane material is prepared by reacting a component A and a component B, wherein the component A and the component B are 100: 40-80 parts by weight, and the component A comprises 1-30 parts by weight of polyether polyol I, 50-90 parts by weight of polyether polyol II, 0-20 parts by weight of polymer polyol, 1-5 parts by weight of a cross-linking agent, 0.5-1 part by weight of a catalyst, 0.5-2 parts by weight of a foam stabilizer, 1.5-2.5 parts by weight of water and 0.1-2 parts by weight of an antioxidant; the component B comprises 10-30 parts of isocyanate and 70-90 parts of modified isocyanate in parts by weight, and the technical scheme better solves the problem.)

1. A high-temperature-resistant and aging-resistant polyurethane material is prepared by reacting a component A and a component B, wherein the component A and the component B are 100: 40-80 parts by weight, and the component A comprises 1-30 parts by weight of polyether polyol I, 50-90 parts by weight of polyether polyol II, 0-20 parts by weight of polymer polyol, 1-5 parts by weight of cross-linking agent, 0.5-1 part by weight of catalyst, 0.5-2 parts by weight of foam stabilizer, 1.5-2.5 parts by weight of water and 0.1-2 parts by weight of antioxidant; the component B comprises 10-30 parts by weight of isocyanate and 70-90 parts by weight of modified isocyanate;

wherein the molecular weight of the polyether polyol I is 3000-8000, the functionality is 2-4, the molecular weight distribution dispersion coefficient is 1.0-1.04, the unsaturation degree is less than or equal to 0.03mmol/g, and the primary hydroxyl content is 80-90%;

the molecular weight of the polyether polyol II is 300-500, the functionality is 2-4, the molecular weight distribution dispersion coefficient is 1.0-1.04, the unsaturation degree is less than or equal to 0.03mmol/g, and the primary hydroxyl content is 80-90%;

the polymer polyol is styrene or acrylonitrile graft copolymerization polyether polyol, the molecular weight is 6000-8000, the functionality is 3, and the solid content is 40-50%;

the cross-linking agent is an alcohol compound or an alcohol amine compound with 2 functionality; the foam stabilizer is at least one of polysiloxane-oxyalkylene block copolymers; the antioxidant is at least one selected from hindered phenols, aromatic secondary amines and benzofuranones.

2. The high temperature and aging resistant polyurethane material of claim 1, wherein the 2-functional alcohol compound is at least one selected from the group consisting of ethylene glycol, 1, 4-butanediol, propylene glycol, and diethylene glycol; the alcohol amine compound is selected from diethanolamine or triethanolamine; the catalyst is selected from at least one of TEDA, DMI, DT, ETS, MR, NP, RX5, TE or TRC; the polysiloxane-oxyalkylene block copolymer is selected from at least one of L-618, B-8715, B-8734, DC-193, L580 or AK 8805; the isocyanate is at least one of PM-200, M20S, MIPS or PAPI-135C; the modified isocyanate is selected from at least one of Suprasec 2412, Suprasec 2424, Suprasec 1075, WANNATE 8215 or WANNATE 8122.

3. The high temperature and aging resistant polyurethane material of claim 1, wherein the hindered phenolic antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], isooctyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, or 2,2' -methylenebis (4-methyl-6-t-butylphenol); the aromatic secondary amine antioxidant is at least one selected from dimethyl-N-phenylaniline, ethyl-N-phenylaniline, N '-diphenyl p-phenylenediamine, N-phenyl-N-cyclohexyl p-phenylenediamine or N-phenyl-N' -isopropyl p-phenylenediamine; the benzofuranones are selected from at least one of 5-tert-butyl-7-methyl-3- (3-methylphenyl) -3-hydro-benzofuran-2-one, 5-tert-butyl-7-methyl-3- (3-methoxyphenyl) -3-hydro-benzofuran-2-one, 5, 7-di-tert-butyl-7-methyl-3- (3-methoxyphenyl) -3-hydro-benzofuran-2-one, or 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3-hydro-benzofuran-one.

4. The high-temperature-resistant and aging-resistant polyurethane material as claimed in claim 1, wherein the component A comprises, by weight, 1-30 parts of polyether polyol I, 50-90 parts of polyether polyol II, 1-20 parts of polymer polyol, 1-5 parts of a crosslinking agent, 0.5-1 part of a catalyst, 0.5-2 parts of a foam stabilizer, 1.5-2.5 parts of water and 0.1-2 parts of an antioxidant; the component B comprises 10-30 parts by weight of isocyanate and 70-90 parts by weight of modified isocyanate.

5. The method for preparing the high temperature and aging resistant polyurethane material according to claim 1, comprising the steps of:

(1) the preparation method comprises the following steps of (1) mixing 1-30 parts of polyether polyol I, 50-90 parts of polyether polyol II, 0-20 parts of polymer polyol, 1-5 parts of cross-linking agent, 0.5-1 part of catalyst, 0.5-2 parts of foam stabilizer, 1.5-2.5 parts of water and 0.1-2 parts of antioxidant, uniformly stirring and mixing, wherein the mixing and stirring temperature is 20-25 ℃, and obtaining a component A;

(2) adding 10-30 parts of isocyanate and 70-90 parts of modified isocyanate according to parts by weight to obtain a component B;

(3) and quickly mixing and uniformly stirring the component A and the component B according to the weight part ratio of 100: 40-80 to obtain the high-temperature-resistant and aging-resistant polyurethane material.

Technical Field

The invention relates to a high-temperature-resistant and aging-resistant polyurethane material and a preparation method thereof.

Background

The application of polyurethane materials in the automobile industry is becoming more and more extensive, and the polyurethane materials become one of the most used plastic varieties in automobiles, and the polyurethane materials for automobiles are developing towards the direction of light weight, safety, environmental protection and comfort. In an emergency, when a person in a vehicle collides with the interior of the vehicle, the polyurethane material can provide better elasticity and buffer property compared with the modified polypropylene hard plastic and the ABS hard plastic, so that the damage is reduced.

In the prior art, when automotive interiors prepared from polyurethane materials are pressed all year round, irradiated by the sun and heated in summer, the compressive strength, the compressive deformation, the tensile strength and the elongation at break of the automotive interiors are reduced, and the normal use of the automotive interiors cannot be ensured, so that the high-temperature-resistant and aging-resistant polyurethane materials for the automotive interiors are urgently needed to be realized.

The aging resistance and the high temperature resistance of the polyurethane material are characterized by the property changes of the tensile strength, the elongation at break and the compressive strength of the polyurethane material under the conditions of high temperature and high humidity.

Chinese patent CN201480047547 discloses a hydrolysis resistant polyurethane article, which is prepared by the following steps: the organic polyisocyanate is mixed with a compound having at least two isocyanate-reactive hydrogen atoms and comprising a polyester polyol and at least one compound obtainable by alkoxylation of an aromatic starter molecule, with a blowing agent, a catalyst and further auxiliaries or additives to give a reaction mixture.

In general, when the core density of the polyurethane material used for the automotive interior is 50 to 80kg/m³In the meantime, the tensile strength of the polyurethane material is generally required to be more than or equal to 100kpa, the elongation at break is more than or equal to 50%, and the compressive strength is more than or equal to 30 kpa; when the tensile strength, the elongation at break and the compressive strength of the polyurethane material meet the above requirements, the molding conditions of the automotive interior ceiling can be satisfied by using the polyurethane material.

Disclosure of Invention

The invention aims to solve the technical problems that a polyurethane material used for automotive interior has poor aging resistance and poor high-temperature resistance, and provides a novel high-temperature-resistant and aging-resistant polyurethane material. The high-temperature-resistant and aging-resistant polyurethane material provided by the invention has the advantages of good aging resistance and good high-temperature resistance. The second technical problem to be solved by the present invention is to provide a preparation method corresponding to the first technical problem. The present invention is also directed to a computer program product for solving the above-mentioned problems.

In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a high-temperature-resistant and aging-resistant polyurethane material is prepared by reacting a component A and a component B, wherein the component A and the component B are 100: 40-80 parts by weight, and the component A comprises 1-30 parts by weight of polyether polyol I, 50-90 parts by weight of polyether polyol II, 0-20 parts by weight of polymer polyol, 1-5 parts by weight of cross-linking agent, 0.5-1 part by weight of catalyst, 0.5-2 parts by weight of foam stabilizer, 1.5-2.5 parts by weight of water and 0.1-2 parts by weight of antioxidant; the component B comprises 10-30 parts by weight of isocyanate and 70-90 parts by weight of modified isocyanate;

wherein the molecular weight of the polyether polyol I is 3000-8000, the functionality is 2-4, the molecular weight distribution dispersion coefficient is 1.0-1.04, the unsaturation degree is less than or equal to 0.03mmol/g, and the primary hydroxyl content is 80-90%;

the molecular weight of the polyether polyol II is 300-500, the molecular weight distribution dispersion coefficient is 1.0-1.04 when the functionality is 2-4, the unsaturation degree is less than or equal to 0.03mmol/g, and the primary hydroxyl content is 80-90%;

the polymer polyol is styrene or acrylonitrile graft copolymerization polyether polyol, the molecular weight is 6000-8000, the functionality is 2-4, and the solid content is 40-50%;

the cross-linking agent is an alcohol compound or an alcohol amine compound with 2 functionality; the antioxidant is at least one selected from hindered phenols, aromatic secondary amines and benzofuranones.

In the above technical solution, preferably, the 2-functional alcohol compound is at least one selected from ethylene glycol, 1, 4-butanediol, propylene glycol, and diethylene glycol; the alcohol amine compound is selected from diethanolamine or triethanolamine; the catalyst is selected from at least one of TEDA, DMI, DT, ETS, MR, NP, RX5, TE or TRC; the polysiloxane-oxyalkylene block copolymer is selected from at least one of L-618, B-8715, B-8734, DC-193, L580 or AK 8805; the isocyanate is at least one of PM-200, M20S, MIPS or PAPI-135C; the modified isocyanate is selected from at least one of Suprasec 2412, Suprasec 2424, Suprasec 1075, WANNATE 8215 or WANNATE 8122.

In the above technical solution, preferably, the hindered phenol antioxidant is at least one selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2,2' -methylenebis (4-methyl-6-tert-butylphenol); the aromatic secondary amine is at least one selected from dimethyl-N-phenylaniline, ethyl-N-phenylaniline, N '-diphenyl-p-phenylenediamine, N-phenyl-N-cyclohexyl-p-phenylenediamine or N-phenyl-N' -isopropyl-p-phenylenediamine; the benzofuranones are selected from at least one of 5-tert-butyl-7-methyl-3- (3-methylphenyl) -3-hydro-benzofuran-2-one, 5-tert-butyl-7-methyl-3- (3-methoxyphenyl) -3-hydro-benzofuran-2-one, 5, 7-di-tert-butyl-7-methyl-3- (3-methoxyphenyl) -3-hydro-benzofuran-2-one, or 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3-hydro-benzofuran-one.

In the above technical solution, preferably, the hindered phenol antioxidant is at least one selected from the group consisting of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2,2' -methylenebis (4-methyl-6-tert-butylphenol); the aromatic secondary amine is at least one selected from dimethyl-N-phenylaniline, ethyl-N-phenylaniline, N '-diphenyl-p-phenylenediamine, N-phenyl-N-cyclohexyl-p-phenylenediamine or N-phenyl-N' -isopropyl-p-phenylenediamine; the benzofuranones are selected from at least one of 5-tert-butyl-7-methyl-3- (3-methylphenyl) -3-hydro-benzofuran-2-one, 5-tert-butyl-7-methyl-3- (3-methoxyphenyl) -3-hydro-benzofuran-2-one, 5, 7-di-tert-butyl-7-methyl-3- (3-methoxyphenyl) -3-hydro-benzofuran-2-one, or 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3-hydro-benzofuran-one.

To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the high-temperature-resistant and aging-resistant polyurethane material comprises the following steps:

(1) the preparation method comprises the following steps of (1) mixing 1-30 parts of polyether polyol I, 50-90 parts of polyether polyol II, 0-20 parts of polymer polyol, 1-5 parts of cross-linking agent, 0.5-1 part of catalyst, 0.5-2 parts of foam stabilizer, 1.5-2.5 parts of water and 0.1-2 parts of antioxidant, uniformly stirring and mixing, wherein the mixing and stirring temperature is 20-25 ℃, and obtaining a component A;

(2) adding 10-30 parts of isocyanate and 70-90 parts of modified isocyanate according to parts by weight to obtain a component B;

(3) and quickly mixing and uniformly stirring the component A and the component B according to the weight part ratio of 100: 40-80 to obtain the high-temperature-resistant and aging-resistant polyurethane material.

According to the invention, the polyether glycol I and the polyether glycol II are combined in the polyurethane composite material, and at least one of hindered phenols, aromatic secondary amines or benzofuranones is matched in the composite material, so that the tensile strength, the elongation at break and the compressive strength of the obtained high-temperature and aging-resistant polyurethane material under the high-temperature and high-humidity condition are not changed greatly from those of the tensile strength, the elongation at break and the compressive strength detected under the conventional condition, therefore, the polyurethane composite material prepared in the invention has the advantages of good aging resistance and good high-temperature resistance when being applied to an automobile ceiling, and a better technical effect is obtained.

Detailed Description

The parameters of polyether polyol I and polyether polyol II used in the examples are shown in Table 1:

TABLE 1 parameters of polyether polyol I and polyether polyol II

Polymer polyol:

polymer polyol 1: the styrene graft copolymerization polyether polyol has the average molecular weight of 6000, the functionality of 3 and the solid content of 45 percent;

polymer polyol 2: the styrene copolymerized polyether polyol has the average molecular weight of 6000, the functionality of 3 and the solid content of 45 percent

Polymer polyol 3: the polymer polyol is polyether polyol of styrene graft copolymerization, and has an average molecular weight of 6000, a functionality of 3 and a solid content of 42%.

Polymer polyol 4: the polyether polyol of styrene graft copolymerization has the average molecular weight of 5000, the functionality of 3 and the solid content of 50 percent.

Polymer polyol 5: the polymer polyol is polyether polyol of styrene graft copolymerization, and has an average molecular weight of 7000, a functionality of 3 and a solid content of 45%.

TABLE 2 raw material List

Example 1

(1) Calculated according to parts by weight, polyether polyol I1: 10 parts of polyether polyol IIA: 80 parts, polymer polyol: 10 parts of crosslinking agent ethylene glycol: 2 parts, catalyst TEDA: 0.5 part, foam stabilizer L-618: 1 part, 2 parts of water, antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester: 0.5 part of the raw materials are uniformly stirred and mixed, and the mixing and stirring temperature is 20 ℃, so that a component A is obtained;

(2) adding isocyanate PM-200 according to parts by weight: 20 parts of modified isocyanate Suprasec 2412: 80 parts of a component B is obtained;

(3) rapidly mixing and uniformly stirring the component A and the component B according to the weight part ratio of 100:50 to obtain a high-temperature-resistant and aging-resistant polyurethane material, wherein the conventional physical property detection data of the prepared high-temperature-resistant and aging-resistant polyurethane material is shown in Table 5; the detection data of the prepared high-temperature-resistant and aging-resistant polyurethane material under the high-temperature and high-humidity conditions are shown in table 6.

Examples 2 to 5

Examples 2 to 5 were carried out according to the procedures of example 1, the only difference being the kind of the reaction raw material, the kind of the catalyst, the mixture ratio of the raw materials, the reaction time and the temperature, which are shown in table 3, and the conventional physical property detection data of the prepared high temperature and aging resistant polyurethane material are shown in table 5; the detection data of the prepared high-temperature-resistant and aging-resistant polyurethane material under the high-temperature and high-humidity conditions are shown in table 6.

Table 3 parts by weight of raw materials for each component in examples 1 to 5 and comparative examples 1 to 2

Examples 6 to 10

Examples 6 to 10 experiments were carried out according to the procedures of example 1, the only differences being the types of the reaction raw materials, the types of the catalysts, the ratios of the raw materials, the reaction time and the temperature, as shown in table 4, and the conventional physical property detection data of the prepared high temperature and aging resistant polyurethane materials are shown in table 5; the detection data of the prepared high-temperature-resistant and aging-resistant polyurethane material under the high-temperature and high-humidity conditions are shown in table 6.

Table 4 parts by weight of raw materials for each component in examples 6 to 10 and comparative examples 3 to 4

Comparative example 1 the procedure of example 1 was followed with the only difference that no antioxidant was added to comparative example 1, as detailed in table 3.

Comparative example 2 the procedure of example 2 was followed with the only difference that no antioxidant was added to comparative example 2, as specified in table 3.

Comparative example 3 the procedure of example 6 was followed with the only difference that no antioxidant was added to comparative example 3, as specified in Table 4.

Comparative example 4 the procedure of example 7 was followed, with the only difference that no antioxidant was added in comparative example 4, as specified in Table 4.

TABLE 5 general physical Property test data of the high temperature and aging resistant polyurethane materials prepared in examples 1 to 10 and comparative examples 1 to 4

Remarking: the conventional physical properties refer to physical data detected at normal temperature of 25 DEG C

TABLE 6 data of the high temperature and high humidity conditions of the high temperature and high aging resistant polyurethane materials prepared in examples 1 to 10 and comparative examples 1 to 4

Remarking: the high temperature and high humidity condition refers to the detection data obtained after treatment at 90 ℃ and 95% humidity.

As can be seen from the table: tensile strength, elongation at break and compressive strength of examples 1 to 10 and comparative examples 1 to 4 measured under conventional conditions were not greatly different; however, after the treatment under high temperature and high humidity conditions, the tensile strength, elongation at break and compressive strength in examples 1 to 10 were not much changed from those measured under conventional conditions, but the tensile strength, elongation at break and compressive strength in comparative examples 1 to 4 were much changed, and the material properties of the polyurethane material formulation without the antioxidant of the present invention were poor in aging resistance and high temperature resistance under high temperature and high humidity conditions.