CN113968958B - Polyurethane and preparation method and application thereof - Google Patents

Polyurethane and preparation method and application thereof Download PDF

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Publication number
CN113968958B
CN113968958B CN202111422600.3A CN202111422600A CN113968958B CN 113968958 B CN113968958 B CN 113968958B CN 202111422600 A CN202111422600 A CN 202111422600A CN 113968958 B CN113968958 B CN 113968958B
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polyurethane
parts
mixing
polysiloxane compound
preparation
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CN113968958A (en
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李光毅
黎庆彬
胡志豪
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Guangdong Fuqiang Technology Co ltd
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Guangdong Fuqiang Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Abstract

The invention provides polyurethane and a preparation method and application thereof. The raw materials for preparing the polyurethane comprise the following components in parts by weight: 50-70 parts of polyether polyol, 10-20 parts of polyester polyol, 60-80 parts of diisocyanate, 5-15 parts of chain extender, 5-10 parts of polysiloxane compound, 1-5 parts of foaming agent and 1-3 parts of ultraviolet light absorber. The polyurethane provided by the invention has good mechanical properties, good thermal stability and weather resistance, and is suitable for preparing automobile instrument boards.

Description

Polyurethane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of automotive interiors, and particularly relates to polyurethane and a preparation method and application thereof.
Background
With the improvement of the living standard of people, the domestic automobile industry rapidly develops, the demand of middle-high-end vehicles is rapidly increased, and the instrument panel is widely focused by people as the most main interior trim part of the automobile. The automobile instrument board refers to a rigid flat board or structural member used for installing various instruments, indicator lights and other devices on an automobile, and comprises a disk, a screen, a cabinet, a table, a simulation semi-simulation disk and the like. The instrument board can be illuminated out of band, can be connected with a console, has various forms and specifications, can be provided with various instruments according to the needs, and can be combined into a whole according to the needs. At present, the automobile instrument panel is almost entirely made of plastics except a small amount of metal, and materials with different properties are prepared for preparing the instrument panel along with the development of the automobile industry and the growth of demands of people.
CN109553750a discloses a process for manufacturing a high-cohesiveness polyurethane automobile instrument board. The preparation raw materials of the high-cohesiveness polyurethane automobile instrument board comprise the following components in parts by weight: 60 to 80 parts of polyether polyol, 10 to 20 parts of polyester polyol, 0.1 to 0.3 part of tertiary amine catalyst, 0.5 to 1.5 parts of silicone oil, 1.5 to 2.5 parts of water, 10 to 15 parts of chain extender, 60 to 70 parts of crude MDI and 30 to 40 parts of liquefied MDI; the preparation process comprises the following steps: (1) Adding polyester polyol, tertiary amine catalyst, water, silicone oil and chain extender into polyether polyol, controlling the rotating speed at 40-80 rpm/min, and stirring for 40-60 min to obtain material A; (2) Mixing and stirring the liquefied MDI and the crude MDI for 30-50 min, and controlling the rotating speed at 30-50 rpm/min to obtain a material B; (3) feeding the material A into a raw material barrel of a foaming machine group A; b, the material B is driven into a material barrel of a B group of a foaming machine; (4) Spreading leather at the bottom of a mould, uniformly mixing the material A and the material B in a mixing area of a mixing head of a casting machine by using a foaming machine, and casting and molding; demolding, and cutting and finishing the polyurethane foam board to obtain an instrument desk shell; (5) And installing the instrument panel to be installed on the instrument desk to finish the manufacturing of the instrument desk. The technical scheme is improved, and the prepared polyurethane automobile instrument board with high cohesiveness is poor in heat stability and weather resistance.
CN108676145a discloses an environment-friendly flame-retardant polyurethane foaming material for instrument panels and a preparation method thereof. The environment-friendly flame-retardant polyurethane foaming material comprises isocyanate and a combined material, wherein the mass ratio of the isocyanate to the combined material is 1:1.7, and the combined material comprises the following components in parts by mass: 3628 60 to 80 parts of polyester, 330 to 45 parts of polyether, 100 to 200 parts of glass fiber, 2056 20 to 30 parts of polyester, 1.5 to 2 parts of silicone oil, 8 to 10 parts of diethanolamine, 1.5 to 1.7 parts of catalyst HP-42, 1 to 1.3 parts of catalyst HP-50, 2.5 to 3.9 parts of water and 33 to 37 parts of flame retardant. The preparation method comprises the following preparation steps: (1) Adding the components of the combined material into a reaction kettle according to the parts by weight for mixing reaction, wherein the reaction temperature is 110-130 ℃, the stirring speed is 100-110 r/min, and the stirring time is 2-3 h, so that the combined material can be obtained; (2) The isocyanate and the composite material are mixed according to the mass ratio of 1:1.7 and react at the temperature of 80-100 ℃ to obtain the environment-friendly flame-retardant polyurethane foaming material for the instrument board. The polyurethane material provided by the technical scheme has better flame retardance, but has poorer heat stability and weather resistance.
CN109535381a discloses a process for manufacturing a low-VOC polyurethane automobile instrument panel. The preparation raw materials of the low-VOC polyurethane automobile instrument panel comprise the following components in parts by weight: 80 to 85 parts of polyether polyol, 1 to 2 parts of vegetable oil, 0.1 to 0.3 part of tertiary amine catalyst, 0.5 to 1.5 parts of silicone oil, 1.5 to 2.5 parts of water, 10 to 15 parts of chain extender, 50 to 70 parts of crude MDI and 15 to 40 parts of liquefied MDI. In the technical scheme, polyether polyol and vegetable oil are used as raw materials, and on the premise of not affecting other performances of the polyurethane automobile instrument board, volatilization of VOC is reduced, environmental protection performance is improved, but the thermal stability and weather resistance of the material are poor.
Therefore, how to provide a polyurethane material with better heat stability and weather resistance and better mechanical property, which is suitable for preparing automobile instrument panels, has become the technical problem to be solved in the present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide polyurethane and a preparation method and application thereof. According to the invention, the organosilicon is introduced into the polyurethane material through the use of the polysiloxane compound, so that the thermal stability of the polyurethane material is improved, and meanwhile, through the matched use of the polysiloxane compound and the ultraviolet light absorber, the weather resistance of the polyurethane material is improved, and the service life of the automobile instrument board prepared by the method is further prolonged.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides polyurethane, wherein the raw materials for preparing the polyurethane comprise the following components in parts by weight:
50-70 parts of polyether polyol, 10-20 parts of polyester polyol, 60-80 parts of diisocyanate, 5-15 parts of chain extender, 5-10 parts of polysiloxane compound, 1-5 parts of foaming agent and 1-3 parts of ultraviolet light absorber.
Polyurethane materials have good wear resistance, solvent resistance and excellent mechanical properties, but have poor thermal stability, and polysiloxane compounds have good heat resistance and hydrolysis resistance. Therefore, in the present invention, the use of the silicone compound introduces the silicone into the polyurethane material, thereby improving the thermal stability of the polyurethane material.
Meanwhile, the polyurethane material with good mechanical properties and high thermal stability is prepared by controlling the weight part of the polysiloxane compound within a specific range. If the weight part of the polysiloxane compound in the polyurethane material is too large, the mechanical property of the prepared polyurethane material is poor due to poor compatibility of the polysiloxane compound and the polyurethane substrate; if the weight portion of the polysiloxane compound in the polyurethane material is too small, the thermal stability of the prepared polyurethane material is poor.
According to the invention, the weather resistance of the polyurethane material is improved through the matched use of the polysiloxane compound and the ultraviolet light absorber. If the raw materials for preparing the polyurethane do not contain a polysiloxane compound or an ultraviolet light absorber, the prepared polyurethane has poor weather resistance.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
As a preferred technical scheme of the invention, the preparation raw materials of the polysiloxane compound comprise the following components in percentage by mass:
30-40% of polydimethylsiloxane, 20-30% of N-cyclohexyl-gamma-aminopropyl trimethoxy silane, 0.5-1% of tetrabutyl titanate and 40-50% of organic solvent.
In the invention, the mass percentage of the polydimethylsiloxane is 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40% and the like.
The mass percentage of the N-cyclohexyl-gamma-aminopropyl trimethoxysilane is 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30% and the like.
The mass percentage of the tetrabutyl titanate is 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%.
The mass percentage of the organic solvent is 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50% and the like.
Preferably, the polydimethylsiloxane is a dihydroxy-terminated polydimethylsiloxane.
Preferably, the number average molecular weight of the dihydroxy-terminated polydimethylsiloxane is 500 to 600, and may be 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, or the like, for example.
Preferably, the organic solvent is toluene.
As a preferred technical scheme of the invention, the preparation method of the polysiloxane compound comprises the following steps:
and mixing polydimethylsiloxane, N-cyclohexyl-gamma-aminopropyl trimethoxy silane, tetrabutyl titanate and an organic solvent, and reacting to obtain the polysiloxane compound.
Preferably, the temperature of the reaction is 90 to 110℃and may be, for example, 90℃92℃94℃96℃98℃100℃102℃104℃106℃108℃110 ℃.
Preferably, the reaction time is 10 to 12 hours, and may be, for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, or the like.
Preferably, the reaction further comprises a post-treatment step.
Preferably, the post-processing method comprises: after cooling, the organic solvent was removed.
In the present invention, the cooling means cooling the reacted reaction system to room temperature.
As a preferred embodiment of the present invention, the polyether polyol is selected from the group consisting of difunctional polyether polyols and/or trifunctional polyether polyols.
The polyether polyol preferably has a number average molecular weight of 2000 to 5000, and may be 2000, 2200, 2500, 2700, 3000, 3300, 3600, 3900, 4200, 4600, 5000, or the like, for example.
Preferably, the polyether polyol has a hydroxyl value of 25 to 40mg KOH/g, and may be, for example, 25mg KOH/g, 26mg KOH/g, 28mg KOH/g, 30mg KOH/g, 32mg KOH/g, 34mg KOH/g, 36mg KOH/g, 38mg KOH/g, 40mg KOH/g, or the like.
Preferably, the polyester polyol is selected from the group consisting of difunctional polyester polyols and/or trifunctional polyester polyols.
The polyester polyol preferably has a number average molecular weight of 1000 to 3000, and may be 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, or the like, for example.
Preferably, the hydroxyl group content of the polyester polyol is 34 to 88mg KOH/g, and may be, for example, 34mg KOH/g, 40mg KOH/g, 46mg KOH/g, 52mg KOH/g, 58mg KOH/g, 64mg KOH/g, 70mg KOH/g, 76mg KOH/g, 82mg KOH/g, 88mg KOH/g, or the like.
As a preferred embodiment of the present invention, the diisocyanate is selected from 4,4' -dicyclohexylmethane diisocyanate and/or diphenylmethane diisocyanate.
Preferably, the chain extender is selected from any one or a combination of at least two of 1, 3-propanediol, 1, 4-butanediol, hexanediol or trimethylolpropane.
Preferably, the foaming agent is water.
Preferably, the ultraviolet light absorber is selected from any one or a combination of at least two of UV-326, UV-327, UV-328, UV-329 or UV-360.
As a preferable embodiment of the present invention, the raw materials for preparing the polyurethane further include 0.5 to 1 part of a catalyst, for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, or the like.
Preferably, the catalyst is a tin-based catalyst.
Preferably, the tin-based catalyst is selected from dibutyltin dilaurate and/or stannous isooctanoate.
In a second aspect, the present invention provides a process for the preparation of a polyurethane as described in the first aspect, the process comprising the steps of:
(1) Mixing polyether polyol, polyester polyol, chain extender, polysiloxane compound, foaming agent, ultraviolet light absorber and catalyst to obtain a mixture;
(2) And (3) mixing the mixture obtained in the step (1) with diisocyanate, and then placing the mixture into a mold for casting molding to obtain the polyurethane.
As a preferable technical scheme of the invention, the mixing method in the step (1) is stirring.
Preferably, the stirring speed is 60 to 120rpm, and may be, for example, 60rpm, 65rpm, 70rpm, 75rpm, 80rpm, 85rpm, 90rpm, 95rpm, 100rpm, 105rpm, 110rpm, 115rpm, 120rpm, or the like.
Preferably, the mixing time is 40-60 min, for example, 40min, 42min, 44min, 46min, 48min, 50min, 52min, 54min, 56min, 58min or 60min, etc.
As a preferable embodiment of the present invention, the mixing method in the step (2) is mixing using a bubbling machine.
Preferably, the casting molding further comprises a post-treatment step.
Preferably, the post-treatment method comprises the following steps: the mold is removed.
In a third aspect, the present invention provides the use of a polyurethane according to the first aspect for the preparation of an automotive dashboard.
Compared with the prior art, the invention has the following beneficial effects:
the polyurethane prepared by the method has good mechanical properties, good thermal stability and weather resistance, tensile strength of 179-192 kPa, elongation at break of 55-62%, thermal decomposition temperature of 283-305 ℃, hydrolysis resistance of 4-5 levels and yellowing resistance of 4-5 levels. The polyurethane provided by the invention is suitable for preparing automobile instrument boards.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Some of the component sources in the examples and comparative examples are as follows:
polyether polyol: DP4000E, national chemical company, inc;
polyester polyol: celluloid chemical industries, inc, PCL220AL;
dihydroxy-terminated polydimethylsiloxane: sigma-Aldrich, CAS number 70131-67-8.
Example 1
The embodiment provides polyurethane and a preparation method thereof, wherein the preparation raw materials of the polyurethane comprise the following components in parts by weight:
60 parts of polyether polyol, 15 parts of polyester polyol, 70 parts of 4,4' -dicyclohexylmethane diisocyanate, 10 parts of 1, 3-propanediol, 6 parts of polysiloxane compound, 3 parts of water, 1 part of UV-326 and 0.8 part of dibutyltin dilaurate;
the preparation raw materials of the polysiloxane compound comprise the following components in percentage by mass:
35% of dihydroxy-terminated polydimethylsiloxane, 24% of N-cyclohexyl-gamma-aminopropyl trimethoxysilane, 1% of tetrabutyl titanate and 40% of toluene;
the preparation method of the polysiloxane compound comprises the following steps:
and mixing polydimethylsiloxane, N-cyclohexyl-gamma-aminopropyl trimethoxy silane, tetrabutyl titanate and toluene, reacting at 100 ℃ for 10 hours, cooling to room temperature, and removing toluene to obtain the polysiloxane compound.
The preparation method of the polyurethane comprises the following steps:
(1) Stirring and mixing polyether polyol, polyester polyol, 1, 3-propylene glycol, a polysiloxane compound, water, UV-326 and dibutyl tin dilaurate for 50min at a rotating speed of 80rpm to obtain a mixture;
(2) And (3) uniformly mixing the mixture obtained in the step (1) with 4,4' -dicyclohexylmethane diisocyanate by using a foaming machine, placing the mixture in a mould for casting and forming, and removing the mould to obtain the polyurethane.
Example 2
The embodiment provides polyurethane and a preparation method thereof, wherein the preparation raw materials of the polyurethane comprise the following components in parts by weight:
50 parts of polyether polyol, 20 parts of polyester polyol, 60 parts of diphenylmethane diisocyanate, 5 parts of 1, 4-butanediol, 7 parts of polysiloxane compound, 1 part of water, 3 parts of UV-327 and 0.5 part of stannous isooctanoate;
the preparation raw materials of the polysiloxane compound comprise the following components in percentage by mass:
30% of dihydroxy-terminated polydimethylsiloxane, 20% of N-cyclohexyl-gamma-aminopropyl trimethoxysilane, 0.5% of tetrabutyl titanate and 49.5% of toluene;
the preparation method of the polysiloxane compound comprises the following steps:
and mixing polydimethylsiloxane, N-cyclohexyl-gamma-aminopropyl trimethoxy silane, tetrabutyl titanate and toluene, reacting at 90 ℃ for 12 hours, cooling to room temperature, and removing toluene to obtain the polysiloxane compound.
The preparation method of the polyurethane comprises the following steps:
(1) Stirring and mixing polyether polyol, polyester polyol, 1, 4-butanediol, polysiloxane compound, water, UV-327 and stannous isooctanoate for 60min at a rotating speed of 60rpm to obtain a mixture;
(2) And (3) uniformly mixing the mixture obtained in the step (1) with diphenylmethane diisocyanate by using a foaming machine, placing the mixture in a mould for casting and forming, and removing the mould to obtain the polyurethane.
Example 3
The embodiment provides polyurethane and a preparation method thereof, wherein the preparation raw materials of the polyurethane comprise the following components in parts by weight:
70 parts of polyether polyol, 10 parts of polyester polyol, 80 parts of 4,4' -dicyclohexylmethane diisocyanate, 15 parts of hexanediol, 8 parts of polysiloxane compound, 5 parts of water, 1 part of UV-328 and 1 part of dibutyltin dilaurate;
the preparation raw materials of the polysiloxane compound comprise the following components in percentage by mass:
39.4% of dihydroxy-terminated polydimethylsiloxane, 20% of N-cyclohexyl-gamma-aminopropyl trimethoxysilane, 0.6% of tetrabutyl titanate and 40% of toluene;
the preparation method of the polysiloxane compound comprises the following steps:
and mixing polydimethylsiloxane, N-cyclohexyl-gamma-aminopropyl trimethoxy silane, tetrabutyl titanate and toluene, reacting at 110 ℃ for 10 hours, cooling to room temperature, and removing toluene to obtain the polysiloxane compound.
The preparation method of the polyurethane comprises the following steps:
(1) Stirring and mixing polyether polyol, polyester polyol, hexanediol, polysiloxane compound, water, UV-328 and dibutyl tin dilaurate for 40min at a rotation speed of 120rpm to obtain a mixture;
(2) And (3) uniformly mixing the mixture obtained in the step (1) with 4,4' -dicyclohexylmethane diisocyanate by using a foaming machine, placing the mixture in a mould for casting and forming, and removing the mould to obtain the polyurethane.
Example 4
The embodiment provides polyurethane and a preparation method thereof, wherein the preparation raw materials of the polyurethane comprise the following components in parts by weight:
65 parts of polyether polyol, 18 parts of polyester polyol, 72 parts of 4,4' -dicyclohexylmethane diisocyanate, 12 parts of trimethylolpropane, 9 parts of polysiloxane compound, 4 parts of water, 2 parts of UV-360 and 1 part of dibutyltin dilaurate;
the preparation raw materials of the polysiloxane compound comprise the following components in percentage by mass:
28% of dihydroxy-terminated polydimethylsiloxane, 24.5% of N-cyclohexyl-gamma-aminopropyl trimethoxysilane, 0.5% of tetrabutyl titanate and 47% of toluene;
the preparation method of the polysiloxane compound comprises the following steps:
and mixing polydimethylsiloxane, N-cyclohexyl-gamma-aminopropyl trimethoxy silane, tetrabutyl titanate and toluene, reacting at 110 ℃ for 11 hours, cooling to room temperature, and removing toluene to obtain the polysiloxane compound.
The preparation method of the polyurethane comprises the following steps:
(1) Stirring and mixing polyether polyol, polyester polyol, trimethylolpropane, polysiloxane compound, water, UV-360 and dibutyltin dilaurate for 45min at a rotation speed of 100rpm to obtain a mixture;
(2) And (3) uniformly mixing the mixture obtained in the step (1) with 4,4' -dicyclohexylmethane diisocyanate by using a foaming machine, placing the mixture in a mould for casting and forming, and removing the mould to obtain the polyurethane.
Example 5
This example provides a polyurethane and a method for producing the same, which are different from example 1 in that the weight part of the silicone compound is 5 parts, and the other conditions are the same as in example 1.
Example 6
This example provides a polyurethane and a method for producing the same, which are different from example 1 in that the weight part of the silicone compound is 10 parts, and the other conditions are the same as in example 1.
Comparative example 1
This comparative example provides a polyurethane and a method for preparing the same, which are different from example 1 in that the weight part of the silicone compound is 2 parts, and the other conditions are the same as in example 1.
Comparative example 2
This comparative example provides a polyurethane and a method for producing the same, which are different from example 1 in that the weight part of the silicone compound is 15 parts, and the other conditions are the same as in example 1.
Comparative example 3
This comparative example provides a polyurethane and a method for producing the same, which are different from example 1 in that the raw material for producing the polyurethane does not contain a polysiloxane compound, the ultraviolet light absorber is 7 parts by weight, and other conditions are the same as in example 1.
Comparative example 4
This comparative example provides a polyurethane and a method for producing the same, which are different from example 1 in that the raw material for producing the polyurethane contains no ultraviolet light absorber, and the silicone compound is 7 parts by weight, and the other conditions are the same as in example 1.
The polyurethane properties provided in the above examples and comparative examples were tested as follows:
tensile strength: DIN EN ISO 1798;
elongation at break: DIN EN ISO 1798;
thermal decomposition temperature: thermogravimetric analysis was performed on the polyurethanes provided in the above examples and comparative examples using a thermogravimetric analyzer, and the temperature at which decomposition starts was recorded;
hydrolysis resistance: GB/T15005-1995;
yellowing resistance: ZN-H/IOS 11507-1997.
The test results of the properties of the foamed polyurethane provided in the above examples and comparative examples are shown in table 1:
TABLE 1
As is clear from Table 1, the polyurethane prepared by the use of the polysiloxane compound and the combination of the polysiloxane compound and the ultraviolet light absorber has good mechanical properties, good thermal stability and weather resistance, the tensile strength of 179-192 kPa, the elongation at break of 55-62%, the thermal decomposition temperature of 283-305 ℃, the hydrolysis resistance of 4-5 levels and the yellowing resistance of 4-5 levels.
If the content of the silicone compound is too small (comparative example 1) as compared with example 1, the thermal stability and weather resistance of the polyurethane prepared are poor; if the content of the silicone compound is too large (comparative example 2), the resulting polyurethane has low tensile strength and elongation at break due to poor compatibility of the silicone compound with the polyurethane matrix. Therefore, the polyurethane prepared by controlling the content of the polysiloxane compound within a specific range has good mechanical properties, heat stability and weather resistance.
Compared with example 1, if the raw materials for preparing the polyurethane do not contain polysiloxane compounds (comparative example 3), the prepared polyurethane has poor thermal stability and weather resistance; if the raw materials for preparing the polyurethane do not contain an ultraviolet light absorber (comparative example 4), the prepared polyurethane has poor weather resistance. Therefore, the polyurethane prepared by the invention has better weather resistance through the matching use of the polysiloxane compound and the ultraviolet light absorber.
In summary, the polyurethane prepared by using the polysiloxane compound and matching the polysiloxane compound with the ultraviolet light absorber has good mechanical property, good thermal stability and weather resistance, and is suitable for preparing automobile instrument boards.
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (27)

1. The polyurethane is characterized by comprising the following raw materials in parts by weight:
50-70 parts of polyether polyol, 10-20 parts of polyester polyol, 60-80 parts of diisocyanate, 5-15 parts of chain extender, 5-10 parts of polysiloxane compound, 1-5 parts of foaming agent and 1-3 parts of ultraviolet light absorber;
the preparation raw materials of the polysiloxane compound comprise the following components in percentage by mass:
30-40% of polydimethylsiloxane,N20-30% of cyclohexyl-gamma-aminopropyl trimethoxysilane, 0.5-1% of tetrabutyl titanate and 40-50% of an organic solvent;
the polydimethylsiloxane is dihydroxy-terminated polydimethylsiloxane;
the preparation method of the polysiloxane compound comprises the following steps:
polydimethyl siloxane,NMixing cyclohexyl-gamma-aminopropyl trimethoxy silane, tetrabutyl titanate and an organic solvent, and reacting to obtain the polysiloxane compound;
the ultraviolet light absorber is selected from any one or a combination of at least two of UV-326, UV-327, UV-328, UV-329 or UV-360.
2. The polyurethane of claim 1, wherein the dihydroxy-terminated polydimethylsiloxane has a number average molecular weight of 500 to 600.
3. The polyurethane of claim 1, wherein the organic solvent is toluene.
4. The polyurethane of claim 1, wherein the reaction temperature is 90-110 ℃.
5. The polyurethane of claim 1, wherein the reaction time is 10 to 12 hours.
6. The polyurethane of claim 1, wherein the post-reaction further comprises a post-treatment step.
7. The polyurethane of claim 6, wherein the post-treatment process comprises: after cooling, the organic solvent was removed.
8. Polyurethane according to claim 1, characterized in that the polyether polyol is selected from the group consisting of difunctional polyether polyols and/or trifunctional polyether polyols.
9. The polyurethane of claim 1, wherein the polyether polyol has a number average molecular weight of 2000 to 5000.
10. The polyurethane of claim 1, wherein the polyether polyol has a hydroxyl number of 25 to 40mg KOH/g.
11. Polyurethane according to claim 1, characterized in that the polyester polyol is selected from the group consisting of difunctional polyester polyols and/or trifunctional polyester polyols.
12. The polyurethane of claim 1, wherein the polyester polyol has a number average molecular weight of 1000 to 3000.
13. The polyurethane of claim 1, wherein the polyester polyol has a hydroxyl content of 34 to 88mg KOH/g.
14. Polyurethane according to claim 1, characterized in that the diisocyanate is selected from 4,4' -dicyclohexylmethane diisocyanate and/or diphenylmethane diisocyanate.
15. The polyurethane of claim 1, wherein the chain extender is selected from any one or a combination of at least two of 1, 3-propanediol, 1, 4-butanediol, hexanediol, or trimethylolpropane.
16. The polyurethane of claim 1, wherein the blowing agent is water.
17. The polyurethane of claim 1, wherein the polyurethane further comprises 0.5-1 part of a catalyst.
18. The polyurethane of claim 17, wherein the catalyst is a tin-based catalyst.
19. Polyurethane according to claim 18, characterized in that the tin-based catalyst is selected from dibutyltin dilaurate and/or stannous isooctanoate.
20. A process for the preparation of a polyurethane as claimed in any one of claims 1 to 19, wherein the process comprises the steps of:
(1) Mixing polyether polyol, polyester polyol, chain extender, polysiloxane compound, foaming agent, ultraviolet light absorber and catalyst to obtain a mixture;
(2) And (3) mixing the mixture obtained in the step (1) with diisocyanate, and then placing the mixture into a mold for casting molding to obtain the polyurethane.
21. The method of claim 20, wherein the mixing in step (1) is by stirring.
22. The method according to claim 21, wherein the stirring speed is 60 to 120 rpm.
23. The method of claim 20, wherein the mixing time is 40-60 minutes.
24. The method of claim 20, wherein the method of mixing in step (2) is mixing using a frother.
25. The method of claim 20, further comprising the step of post-treatment after the casting.
26. The method of claim 25, wherein the post-treatment is performed by: the mold is removed.
27. Use of a polyurethane according to any one of claims 1 to 19 for the preparation of automotive dashboards.
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