CN109942775B - Fiber-reinforced polyurethane resin composition for automobile exterior trimming parts and preparation method thereof - Google Patents
Fiber-reinforced polyurethane resin composition for automobile exterior trimming parts and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fiber reinforced polyurethane resin composition for automobile exterior trimming parts and a preparation method thereof, wherein the fiber reinforced polyurethane resin composition comprises A, B components, wherein the component B is polyisocyanate, and the component A comprises polyether polyol 1, polyether polyol 2, polyether polyol 3, a chain extender, a foaming agent, a composite catalyst, a flame retardant, an antioxidant and a foam stabilizer; the polyether polyol 1 is prepared by polymerizing propylene oxide by taking pentaerythritol as an initiator; the polyether polyol 2 is prepared by polymerizing propylene oxide by using sorbitol and glycerol as initiators; the polyether polyol 3 is prepared by polymerizing organic silicon modified phenolic resin and activated melamine serving as composite initiators and propylene oxide serving as a polymerization monomer at 90-110 ℃ in the presence of an alkaline catalyst; the composite catalyst is a composition of an intumescent catalyst, a gel catalyst and a polymerization catalyst. The polyurethane material prepared from the resin composition has good dimensional stability and excellent mechanical properties.
Description
Technical Field
The invention relates to the field of polyurethane, in particular to fiber reinforced polyurethane resin for automobile exterior trimming parts.
Background
With the development of the automobile industry and the improvement of environmental protection laws and regulations, more and more automobile enterprises realize energy conservation and emission reduction through automobile lightweight, the pursuit of safety is higher and higher while the lightweight is realized, and the automobile exterior trimming part plays a vital role as the first safety guarantee of the automobile.
Polyurethane rigid foams have been widely used in the automotive field because of their light weight and excellent physical properties such as heat resistance and mechanical properties. In order to ensure the safety of vehicles, fiber-reinforced composite materials are generally prepared by impregnating materials such as glass fibers and carbon fibers with a urethane resin, and are used after further improving the mechanical strength thereof. Automotive exterior parts must have good dimensional stability and excellent mechanical properties because they are subjected to the influence of the external weather for a long period of time.
Patent document CN107735421A discloses a rigid polyurethane composition, a rigid polyurethane resin, a molded article and a fiber reinforced plastic, the present invention is characterized in that the rigid polyurethane composition is prepared by using alicyclic polyisocyanate which accounts for 10-70% of polyisocyanate component, but the alicyclic polyisocyanate does not contain phenyl group, so the heat resistance is not good, and as a reinforcing material, carbon fiber with high cost is used, which is not beneficial to industrial production and application.
Patent document CN105199075A discloses a polyurethane composite material and a preparation method thereof, which is characterized in that the polyurethane composite material is prepared by curing through radical polymerization. However, the prepared polyurethane low-viscosity resin is pasty and is not beneficial to combination and infiltration with glass fibers, the free radical polymerization reaction condition is harsh, the problem of oxygen inhibition exists, and the preparation process of the later-stage composite material is relatively complex.
Patent document CN104177581A discloses a polyurethane composition for polyurethane composites. The polyurethane rigid foam prepared by using the conventional polyether polyol and polyester polyol with low functionality has poor dimensional stability of products.
Disclosure of Invention
The first technical problem solved by the invention is to provide a fiber-reinforced polyurethane resin composition for automobile exterior parts, and a polyurethane material prepared from the resin composition has good dimensional stability and excellent mechanical properties.
The second technical problem solved by the invention is to provide a preparation method of the composition.
In order to solve the first technical problem, the invention provides a fiber-reinforced polyurethane resin composition for automobile exterior parts, which comprises a component A and a component B, wherein the component B is polyisocyanate, and the component A comprises the following components in parts by weight:
polyether polyol 1: 50-65 parts;
polyether polyol 2: 15-25 parts;
polyether polyol 3: 5-10 parts;
chain extender: 5-10 parts;
foaming agent: 0.1-5 parts;
a composite catalyst: 0.1-3 parts;
flame retardant: 1-10 parts;
antioxidant: 0.1-2 parts;
foam stabilizer: 0.1-2 parts.
The weight ratio of the component A to the component B is 1: 1.3-1.6, preferably 1: 1.4-1.5.
The polyether polyol 1 adopts pentaerythritol as an initiator, a polymerization unit is propylene oxide, the hydroxyl value is 300-450 mgKOH/g, the preferable hydroxyl value is 350-400 mgKOH/g, the average functionality is 3-5, and the preferable functionality is 4.
The polyether polyol 2 adopts sorbitol and glycerol as initiators, a polymerization unit is propylene oxide, the hydroxyl value is 400-550 mg KOH/g, preferably 400-500 mg KOH/g, the average functionality is 5-7, and preferably the functionality is 6.
The polyether polyol 3 has an average functionality of 3-5 and a hydroxyl value of 300-500 mg KOH/g, and can be prepared by the following method: the organic silicon modified phenolic resin and activated melamine are used as composite initiators, propylene oxide is used as a polymerization monomer, and the organic silicon modified phenolic resin and the activated melamine are polymerized at 90-110 ℃ in the presence of an alkaline catalyst, wherein the polymerization temperature is preferably 100 ℃. The preferable mass ratio of the organic silicon modified phenolic resin to the activated melamine is 1: 10-10: 1.
The organic silicon modified phenolic resin can be prepared from organic silicon modified phenol and formaldehyde aqueous solution under the condition of an alkaline catalyst, the polymerization temperature is 70-90 ℃, the polymerization time is 4-6 h, and water is removed after the reaction is finished. The organic silicon modified phenol is prepared by carrying out addition reaction on tetramethyldisiloxane and o-alkenylphenol at 50-60 ℃ for 3-4 h by adopting a platinum catalyst. The mass concentration of the formaldehyde aqueous solution is preferably 37%. The basic catalyst is preferably dimethylethanolamine.
The activated melamine is prepared by mixing melamine and formaldehyde aqueous solution in an alcohol solvent, adding an alkaline catalyst, stirring and heating to 80 ℃ for reaction for 3 hours, and removing water after the reaction is finished. The aqueous formaldehyde solution preferably has a mass concentration of 37%. The basic catalyst is preferably NaOH.
The basic catalyst of the present invention is one or more of NaOH, KOH, ammonia, aniline, triethylamine, dimethylethanolamine, etc.
The composite catalyst is a composition of an intumescent catalyst, a gel catalyst and a polymerization catalyst. Wherein the foaming catalyst is selected from one or more of pentamethyl diethylene triamine, bis-dimethyl aminoethyl ether, N-methyl dicyclohexylamine, modified bis (dimethylaminoethyl) ether, tetramethyl hexamethylene diamine and the like; the gel-type catalyst is selected from one or more of tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyl tin dilaurate, dibutyl tin dithiolate, dibutyl tin maleate and the like; the polymerization catalyst is selected from one or more of (2-hydroxypropyl) trimethyl ammonium formate, ethyl quaternary ammonium salt, octyl quaternary ammonium salt and the like; preferably, the foaming catalyst is pentamethyldiethylenetriamine, the gelling catalyst is dibutyl tin dilaurate, and the polymerization catalyst is (2-hydroxypropyl) trimethyl ammonium formate. The mass ratio of the gel-type catalyst, the foam-type catalyst and the polymerization catalyst is preferably 2: 1.
The chain extender is one or more of ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol and the like; ethylene glycol is preferred.
The foaming agent is water and N2、CO2One or more of chlorofluorocarbon compounds, hydrochlorofluorocarbon compounds, or the like; preferably water.
The flame retardant may be generally known in the art. Suitable flame retardants such as brominated esters; a brominated ether; or brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol; and chlorinated phosphoric esters such as tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate (TCPP), tris (1, 3-dichloropropyl) phosphate, tricresyl phosphate, tris (2, 3-dibromopropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, dimethyl methylphosphonate, diethyl diethanoylaminomethylphosphonate; or other phosphates or phosphonates, such as diethyl ethylphosphonate (DEEP), triethyl phosphate (TEP), dimethyl propylphosphonate (DMPP) or cresyldiphenyl phosphate (DPK), as flame retardants; preferably TCPP.
The antioxidant may be one or more of a hindered phenol-based antioxidant, a phosphorus-based antioxidant, and the like. Examples of the hindered phenol-based antioxidant include 4-methyl-2, 6-di-tert-Butylphenol (BHT), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the like; the phosphorus-based antioxidant may be one or more of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite), and the like; preferably tris (2-ethylhexyl) phosphite.
The foam stabilizer refers to a material that promotes the formation of a regular pore structure during foaming. The foam stabilizer is silicone oil containing Si-C bonds, the Si-C bonds are not easy to hydrolyze, the foaming stability and the long-term storage stability of the polyether composition can be effectively improved, and the stability of the polyurethane rigid foam plastic containing the polyether composition can be further improved. The silicone oil is one or more silicone oils selected from the group consisting of L-6863, L-6989, L-6952 or L-6900 from Mitigo advanced materials, AK8812 or AK8809 from Demeishi; l-6989 is preferred.
The fiber reinforced material is selected from one of glass fiber felt, glass fiber cloth, carbon fiber cloth, aromatic polyamide fiber fabric, natural fiber fabric, glass fiber, carbon fiber, polyester fiber, natural fiber (such as cotton, sisal, jute, hemp, reed, flax fiber and the like), aromatic polyamide fiber, nylon fiber, basalt fiber, boron fiber, silicon carbide fiber, asbestos fiber, whisker, hard particles, metal fiber and the like; glass fibers are preferred.
The isocyanate component B is aromatic polyisocyanate, and comprises one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and corresponding isomer mixture, 4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate and the like. Preferably polymethylene polyphenyl polyisocyanates; preferably BASF M20S.
In order to solve the second technical problem, the invention provides a preparation method of a fiber-reinforced polyurethane resin composition for automobile exterior parts, comprising the following steps: and (2) component A: adding the metered polyether polyol 1, polyether polyol 2, polyether polyol 3, a chain extender, a foaming agent, a catalyst composition, a flame retardant, an antioxidant and a foam stabilizer into a reaction kettle, and mixing and stirring for 4 hours at 40 ℃ to prepare the polyurethane foam; the component B is polyisocyanate.
The polyurethane resin composition of the present invention can be used for preparing a polyurethane composite material by a casting process. The casting process can use any known process in the field, preferably a high-pressure casting machine of German Claus Ma Fei group company, and is prepared by a reaction forming process of long glass fiber reinforced polyurethane, which is well known by operators, such as controlling the temperature of the component A and the component B to be 22-26 ℃ and casting the components in a mold without plates or coated with ABS plates.
By adopting the preparation method of the polyurethane resin composition and the composite material, the prepared polyurethane composite material has good dimensional stability and excellent mechanical properties.
The polyurethane composite material provided by the invention can be applied to automobile exterior trimming part products, and comprises the following components: front and rear bumpers of a motor vehicle, mud guards of the motor vehicle, radiator grids of the motor vehicle, cross beams of the motor vehicle and the like.
Detailed Description
The following examples are provided to better illustrate the effects of the present invention, but the present invention is not limited to the examples.
The contents of the respective components in examples and comparative examples are in units of parts by weight of the raw materials except for the specific ones. The invention is now further illustrated by the following examples, but is not limited thereto.
The raw materials used in the examples:
polyether polyol 1: pentaerythritol is used as an initiator, a polymerization unit is propylene oxide, the hydroxyl value is 380mgKOH/g, and the functionality is 4.
Polyether polyol 2: sorbitol and glycerol were used as initiators, the polymerization unit was propylene oxide, the hydroxyl number was 500mg KOH/g, and the functionality was 5.8.
Polyether polyol 3-1:
(1) synthesis of silicone-modified phenolic polymer: 1kg of tetramethyldisiloxane was mixed with 2kg of o-allylphenol in 5kg of toluene solution, and 0.06g H was added2PtCl6And (3) carrying out addition reaction on the catalyst at 60 ℃ for 4h, and after the reaction is finished, carrying out rotary evaporation on water at 110 ℃ to prepare the organic silicon modified phenolic polymer S1.
(2) Preparation of low-polymerization-degree phenolic resin: 2.42kg of S1, 1.15kg of formaldehyde, 5g of ammonia water, 10g of aniline and 1kg of water are added into a 10L glass flask, the mixture is stirred and reacted for 6 hours at the temperature of 90 ℃, and after the reaction is finished, the moisture is removed under the vacuum condition of 100 ℃ to prepare the low-polymerization-degree phenolic resin S2.
(3) Preparation of activated melamine: 1.5kg of melamine, 1kg of formaldehyde, 0.25kg of methanol, 0.5kg of water and 2.5g of NaOH are added into a 5L glass flask, the mixture is stirred and reacted for 3 hours at the temperature of 80 ℃, and after the reaction is finished, the water is removed under the vacuum condition at the temperature of 100 ℃ to prepare the activated melamine S3.
(4) 0.6kg of S2 low-polymerization-degree phenolic resin, 1kg of S3 activated melamine and 60g of dimethylethanolamine are added into a 10L glass flask, nitrogen is introduced for replacement, the mixture is stirred and reacted at 100 ℃, 6kg of propylene oxide is slowly added for polymerization, and the polyether polyol 3-1 is prepared. Hydroxyl number 380mg/KOH, functionality 3.5.
Polyether polyol 3-2: 1kg of S2 low-polymerization-degree phenolic resin, 0.6kg of S3 activated melamine and 60g of dimethylethanolamine are added into a 10L glass flask, nitrogen is introduced for replacement, the mixture is stirred and reacts at 100 ℃, 6kg of propylene oxide is slowly added for polymerization, and the homemade polyether polyol 3-2 is prepared. Hydroxyl number 372mg/KOH, functionality 4.
Polyether polyol 3-3: 0.8kg of S2 low-polymerization-degree phenolic resin, 0.8kg of S3 activated melamine and 60g of dimethylethanolamine are added into a 10L glass flask, nitrogen is introduced for replacement, the mixture is stirred and reacted at 100 ℃, 6kg of propylene oxide is slowly added for polymerization, and the self-made polyether polyol 3-3 is prepared. Hydroxyl number 368mg/KOH, functionality 3.7.
Chain extender: ethylene glycol
Foaming agent: water (W)
Gel catalyst: dibutyl tin dilaurate
Foaming catalyst: pentamethyldiethylenetriamine
Trimerization catalyst: (2-hydroxypropyl) trimethyl ammonium formate
Flame retardant: TCPP
Antioxidant: phosphorous acid tri (2-ethylhexyl) ester
Foam stabilizer: l-6989
Polyisocyanate: BASF M20S
Table 1 shows the example and comparative example formulations.
Preparation of polyurethane rigid foam material products: the raw materials are uniformly mixed according to the weight parts shown in the table 1 to prepare a component A, and a component B is BASF M20S. The temperature of the composition A prepared in the examples 1-3 and the composition B prepared in the comparative example 1 is controlled to be (25 +/-3) DEG C, the composition A and the composition B are poured into a mold covered with an ABS plate and having the mold temperature of 50-60 ℃ by a high-pressure pouring machine of Claus Ma Fei group company of Germany, the glass fiber content is 25%, and the mass ratio of the composition A to the composition B is 1: 1.4, and the composition A and the composition B are opened after the mold is closed for 8min, so that a polyurethane hard material product is prepared. Relevant mechanical properties were tested after 7 days of maturation at (25. + -. 3) ℃ C. The properties of the article are shown in Table 2.
TABLE 1 example and comparative example formulations
TABLE 2 comparison of free foam and article data obtained in examples and comparative examples
As can be seen from the data in the examples and comparative examples in Table 2, the bending strength, tensile strength and impact strength of the product obtained by using the polyether polyol prepared by the organosilicon modified phenolic resin are obviously improved, and the water resistance and the dimensional stability at high and low temperatures of the product are also improved.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. A fiber-reinforced polyurethane resin composition for automobile exterior parts comprises a component A and a component B, wherein the component B is polyisocyanate, and the component A comprises the following components in parts by weight
Polyether polyol 1: 50-65 parts;
polyether polyol 2: 15-25 parts;
polyether polyol 3: 5-10 parts;
chain extender: 5-10 parts;
foaming agent: 0.1-5 parts;
a composite catalyst: 0.1-3 parts;
flame retardant: 1-10 parts;
antioxidant: 0.1-2 parts;
foam stabilizer: 0.1-2 parts;
the weight ratio of the component A to the component B is 1: 1.3-1.6;
the polyether polyol 1 adopts pentaerythritol as an initiator, a polymerization unit is propylene oxide, the hydroxyl value is 300-450 mgKOH/g, and the average functionality is 4;
the polyether polyol 2 adopts sorbitol and glycerol as initiators, a polymerization unit is propylene oxide, the hydroxyl value is 400-550 mg KOH/g, and the average functionality is 5-7;
the polyether polyol 3 has an average functionality of 3-5 and a hydroxyl value of 300-500 mg KOH/g, and is prepared by the following method: the organic silicon modified phenolic resin and activated melamine are used as composite initiators, propylene oxide is used as a polymerization monomer, and the organic silicon modified phenolic resin and the activated melamine are polymerized at 90-110 ℃ in the presence of an alkaline catalyst; the mass ratio of the organic silicon modified phenolic resin to the activated melamine is 1: 10-10: 1;
the composite catalyst is a composition of a foaming catalyst, a gel catalyst and a polymerization catalyst;
the organic silicon modified phenolic resin is prepared from organic silicon modified phenol and formaldehyde aqueous solution under the condition of an alkaline catalyst, the polymerization temperature is 90 ℃, the polymerization time is 6 hours, and the moisture is removed after the reaction is finished;
the organic silicon modified phenol is prepared by carrying out addition reaction on tetramethyldisiloxane and o-alkenylphenol at 60 ℃ for 4h by adopting a platinum catalyst.
2. The fiber-reinforced polyurethane resin composition for automobile exterior parts according to claim 1, wherein the mass concentration of the aqueous formaldehyde solution is 37%, and the basic catalyst is dimethylethanolamine.
3. The fiber-reinforced polyurethane resin composition for automobile exterior parts according to claim 1, wherein the activated melamine is prepared by mixing melamine and formaldehyde aqueous solution in an alcohol solvent, adding an alkaline catalyst, stirring and heating to 80 ℃ for reaction for 3 hours, and removing water after the reaction is finished.
4. The fiber-reinforced polyurethane resin composition for automobile exterior parts according to claim 3, wherein the aqueous formaldehyde solution has a mass concentration of 37%; the alkaline catalyst is NaOH.
5. The fiber-reinforced polyurethane resin composition for automobile exterior parts according to claim 1 or 3, wherein the basic catalyst is one or more of NaOH, KOH, ammonia water, aniline, triethylamine, and dimethylethanolamine.
6. The fiber-reinforced polyurethane resin composition for automobile exterior parts according to claim 1, the blowing catalyst is selected from one or more of pentamethyldiethylenetriamine, bis-dimethylaminoethyl ether, N-methyldicyclohexylamine, modified bis (dimethylaminoethyl) ether and tetramethylhexamethylenediamine; the gel-type catalyst is selected from one or more of tin acetate, tin octoate, tin oleate, tin laurate, dibutyl tin diacetate, dimethyl tin dilaurate, dibutyl tin dithiolate and dibutyl tin maleate; the polymerization catalyst is selected from one or more of (2-hydroxypropyl) trimethyl ammonium formate, ethyl quaternary ammonium salt or octyl quaternary ammonium salt; the mass ratio of the gel catalyst, the foaming catalyst and the polymerization catalyst is 2: 1.
7. The fiber-reinforced polyurethane resin composition for automobile exterior parts according to claim 1, wherein the chain extender is one or more of ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, and pentaerythritol; the foaming agent is water and N2、CO2One or more of a chlorofluorocarbon compound or a hydrochlorofluorocarbon compound; the antioxidant is one or more of hindered phenol antioxidant and phosphorus antioxidant; the foam stabilizer is selected from one or more of silicone oil with the model number of L-6863, L-6989, L-6952 or L-6900 of Mitigo advanced materials company, AK8812 or AK8809 of Germany and American world company; the fiber reinforced material is selected from glass fiber felt, glass fiber cloth, carbon fiber cloth, aromatic polyamide fiber fabric and natural fiberOne of fiber fabric, glass fiber, carbon fiber, polyester fiber, natural fiber, nylon fiber, basalt fiber, boron fiber, silicon carbide fiber, asbestos fiber, whisker, hard particle and metal fiber; the component B is aromatic polyisocyanate.
8. The fiber-reinforced polyurethane resin composition for automobile exterior parts according to claim 7, wherein the nylon fiber is an aromatic polyamide fiber.
9. A method for preparing the fiber-reinforced polyurethane resin composition for automobile exterior parts according to any one of claims 1 to 8, comprising the steps of: and (2) component A: adding the metered polyether polyol 1, polyether polyol 2 and polyether polyol 3, a chain extender, a foaming agent, a composite catalyst, a flame retardant, an antioxidant and a foam stabilizer into a reaction kettle, and mixing and stirring for 4 hours at 40 ℃ to prepare the polyurethane foam; the component B is used as it is.
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| CN111004379B (en) * | 2019-12-02 | 2022-03-15 | 浙江理工大学桐乡研究院有限公司 | Preparation method of flame-retardant polyol with high phosphorus content and multiple functionality degrees |
| CN111499828B (en) * | 2020-04-15 | 2022-04-12 | 黎明化工研究设计院有限责任公司 | Resin composition for low-density high-flame-retardant polyurethane material and application thereof |
| WO2021233765A1 (en) * | 2020-05-18 | 2021-11-25 | Basf Se | A polyurethane-forming system, a composite comprising the polyurethane-forming system and a fiber-reinforced material, a process for the production of the composite, and the use of the composite |
| CN113881077A (en) * | 2021-11-18 | 2022-01-04 | 扬州万盛实业有限公司 | Production method of light-weight carriage framework and carriage plate framework |
| CN115058113A (en) * | 2022-07-08 | 2022-09-16 | 重庆欧典实业有限公司 | Fiber-reinforced polyurethane composite material and preparation method and application thereof |
| CN115232277B (en) * | 2022-08-11 | 2023-09-22 | 山东一诺威新材料有限公司 | Special polyether polyol for emulsion-like polyurethane soft foam and preparation method thereof |
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