CN111423555A - High-temperature-resistant and aging-resistant polyurethane foam and preparation method and application thereof - Google Patents
High-temperature-resistant and aging-resistant polyurethane foam and preparation method and application thereof Download PDFInfo
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- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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Abstract
The invention relates to high-temperature-resistant and aging-resistant polyurethane foam, and a preparation method and application thereof, and mainly solves the technical problems of poor aging resistance and poor high-temperature resistance of polyurethane foam for automobile armrests in the prior art. The high-temperature-resistant and aging-resistant polyurethane foam 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 of isocyanate and 70-90 parts of modified isocyanate by weight, so that the problem is better solved, and the modified isocyanate can be used for the production of the automobile armrest.
Description
Technical Field
The invention relates to high-temperature-resistant and aging-resistant polyurethane foam and a preparation method and application 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 foam materials for automobiles are developing towards the direction of light weight, safety, environmental protection and comfort. As an important component in automobile interior decoration, in an emergency, when an occupant collides with the automobile armrest, the polyurethane foam and the modified polypropylene hard plastic can provide better elasticity and cushioning property compared with ABS hard plastic, so that damage is reduced.
In the prior art, when an automobile armrest prepared from a polyurethane foam material is pressed all the year round, is irradiated by the sun and is heated in summer, the compression strength, the compression deformation, the tensile strength and the elongation at break of the automobile armrest are reduced, and the normal use of the automobile armrest cannot be ensured, so that the high-temperature-resistant and aging-resistant polyurethane foam material for the automobile armrest is urgently needed.
The aging resistance and high temperature resistance of the polyurethane foam are characterized by the property changes of tensile strength, elongation at break and compression strength of the polyurethane foam under the conditions of high temperature and high humidity.
Chinese patent CN103936957B discloses an antibacterial polyurethane self-skinning foam composition for a seat armrest, which is composed of combined polyether, an antibacterial agent and isocyanate, so that the antibacterial polyurethane self-skinning foam composition has excellent antibacterial performance and excellent skinning performance, and the antibacterial rate II is more than or equal to 90%.
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.
Under normal conditionsThe polyurethane foam for the automobile armrest has a core density of 50-80 kg/m3In the meantime, the tensile strength of the polyurethane foam 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, elongation at break and compressive strength of the polyurethane foam satisfy the above requirements, the molding conditions of the automobile interior armrest can be satisfied using the polyurethane foam.
Disclosure of Invention
The invention provides a novel high-temperature-resistant and aging-resistant polyurethane foam, which aims to solve the technical problems of poor aging resistance and poor high-temperature resistance of the polyurethane foam used in an automobile armrest. The high-temperature-resistant and aging-resistant polyurethane foam 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 foam 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 selected from at least one of ethylene glycol, 1, 4-butanediol, propylene glycol or diethylene glycol, the alkanolamine 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-alkylene oxide block copolymer is selected from at least one of L-618, B-8715, B-8734, DC-193, L580 or AK8805, the isocyanate is selected from at least one of PM-200, M20S, MIPS or PAPI-135C, and the modified isocyanate is selected from at least one of Suprasec2412, Suprasec 2424, Suprasec1075, WANNATE 8215 or wannnate 8122.
In the above embodiment, the hindered phenol antioxidant is preferably at least one selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], isooctanol β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 2,2' -methylenebis (4-methyl-6-tert-butylphenol), at least one selected from secondary aromatic amines selected from dimethyl-N-phenylaniline, ethyl-N-phenylaniline, N ' -diphenyl-p-phenylenediamine, N-phenyl-N-cyclohexylp-phenylenediamine and N-phenyl-N ' -isopropyl-p-phenylenediamine, and at least one selected from 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 and 5, 7-di-tert-butyl-7-methyl-3- (3-methoxyphenyl) -3-hydro-benzofuran-2-one.
In the above embodiment, the hindered phenol antioxidant is preferably at least one selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 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-cyclohexylp-phenylenediamine or N-phenyl-N ' -isopropyl-p-phenylenediamine, and the benzofuranone is at least one selected from 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-di-tert-butyl-7-methyl-3- (3-methoxyphenyl) -3-hydro-benzofuran-2-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 foam 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 foam.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the high-temperature-resistant and ageing-resistant polyurethane foam is applied to automobile handrails.
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 foam under the high-temperature and high-humidity condition are not greatly changed 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 automobile armrests, 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) According to the weight portion, 1: 10 portions of polyether polyol I, 80 portions of polyether polyol IIA, 10 portions of polymer polyol, 2 portions of cross-linking agent ethylene glycol, 0.5 portion of catalyst TEDA, 1 portion of foam stabilizer L-618, 2 portions of water, 0.5 portion of antioxidant tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the components A are obtained after the components are uniformly stirred and stirred at the temperature of 20 ℃;
(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) after the component A and the component B are quickly mixed and uniformly stirred according to the weight part ratio of 100:50, the high-temperature-resistant and aging-resistant polyurethane foam material is obtained, and the conventional physical property detection data of the prepared high-temperature-resistant and aging-resistant polyurethane foam material is shown in Table 5; the detection data of the prepared high-temperature-resistant and aging-resistant polyurethane foam material under the high-temperature and high-humidity conditions are shown in table 6;
(4) the prepared high-temperature-resistant and aging-resistant polyurethane foam material is applied to automobile armrests.
Examples 2 to 5
Examples 2 to 5 were conducted in accordance with the procedures of example 1, with 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, as shown in table 3, and the conventional physical property test data of the high temperature and aging resistant polyurethane foam prepared is shown in table 5; the test data of the prepared high temperature and aging resistant polyurethane foam under high temperature and high humidity conditions are shown in table 6, and examples 1 to 5 and comparative examples 1 to 2 are all applied to the automobile armrest.
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 conducted in accordance with the procedures of example 1, with 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, as shown in table 4, and the conventional physical property test data of the prepared high temperature and aging resistant polyurethane foam is shown in table 5; the test data of the prepared high temperature and aging resistant polyurethane foam under high temperature and high humidity conditions are shown in table 6, and examples 6 to 10 and comparative examples 3 to 4 are all applied to the automobile armrest.
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 foams 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 measurements of the high temperature and high humidity conditions of the high temperature and high aging resistant polyurethane foams 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 foam properties of the polyurethane foam formulation without the antioxidant of the present invention were poor in aging resistance and high temperature resistance under high temperature and high humidity conditions.
Claims (6)
1. A high-temperature-resistant and aging-resistant polyurethane foam 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 polyether polyol of styrene or acrylonitrile graft copolymer, and the molecular weight is 6000 to
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 foam according to claim 1, wherein the 2-functional alcohol compound is at least one selected from ethylene glycol, 1, 4-butanediol, propylene glycol or diethylene glycol, the alkanolamine compound is diethanolamine or triethanolamine, the catalyst is at least one selected from TEDA, DMI, DT, ETS, MR, NP, RX5, TE or TRC, the polysiloxane-alkylene oxide block copolymer is at least one selected from L-618, B-8715, B-8734, DC-193, L580 or 8805, the isocyanate is at least one selected from PM-200, M20S, MIPS or PAPI-135C, and the modified isocyanate is at least one selected from SUPRASEC2412, SUPRASEC 2424, SUPRASEC1075, WANNATE 8215 or WANNATE 8122.
3. The high temperature and aging resistant polyurethane foam according to claim 1, wherein the hindered phenolic 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 antioxidant is at least one selected from dimethyl-N-phenylaniline, ethyl-N-phenylaniline, N ' -diphenyl-p-phenylenediamine, N-phenyl-N-cyclohexylp-phenylenediamine and N-phenyl-N ' -isopropyl-p-phenylenediamine, and the benzofuranone is at least one selected from 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 and 5, 7-di-tert-butyl-3-methyl-3- (3-hydroxyphenyl) -3-di-hydro-benzofuran-2-one.
4. The high-temperature-resistant and aging-resistant polyurethane foam 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 of making a high temperature resistant, aging resistant polyurethane foam of 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 foam.
6. The high temperature and aging resistant polyurethane foam of claim 1 applied in an automobile armrest.
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| CN202011625115.1A CN112574382A (en) | 2020-04-29 | 2020-12-30 | High-temperature-resistant and aging-resistant polyurethane material and preparation method thereof |
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| CN113292696A (en) * | 2021-05-27 | 2021-08-24 | 上海凯众汽车零部件有限公司 | High-temperature-resistant polyurethane foam material, and preparation method and application thereof |
| CN115703874A (en) * | 2021-08-11 | 2023-02-17 | 江苏赛胜新材料科技有限公司 | High-temperature-resistant polyurethane plate foaming material and preparation method and application thereof |
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| CN106632963A (en) * | 2016-12-30 | 2017-05-10 | 江苏长顺高分子材料研究院有限公司 | Automobile roof polyurethane composition |
| CN109666112A (en) * | 2018-12-12 | 2019-04-23 | 无锡吉兴木桥高分子材料科技有限公司 | A kind of roof of the vehicle polyurethane foam and preparation method thereof |
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| CN113292696A (en) * | 2021-05-27 | 2021-08-24 | 上海凯众汽车零部件有限公司 | High-temperature-resistant polyurethane foam material, and preparation method and application thereof |
| CN115703874A (en) * | 2021-08-11 | 2023-02-17 | 江苏赛胜新材料科技有限公司 | High-temperature-resistant polyurethane plate foaming material and preparation method and application thereof |
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