Preparation method of polyurethane foam composite PMMA / ABS structural plate

Abstract

This case involves a method for preparing polyurethane foam composite PMMA / ABS structural panels. The preparation of polyol composition A involves adding polyol, chain extender, crosslinker, dicyclopentadiene, blowing agent, catalyst, and stabilizer to a reaction kettle according to metered amounts and stirring for 30 to 60 minutes at room temperature and pressure until uniformly mixed. Polyol composition A and isocyanate component B are then mixed at a ratio of A:B = 100:150 to 170, sprayed into a mold, a PMMA / ABS sheet is placed on the mold, and the mold is closed and pressure maintained for 7 minutes. The polyurethane foam used in polyurethane foam composite PMMA / ABS special structural panels is prepared using all-water foaming. The polyurethane foam prepared by the present invention exhibits excellent mechanical properties, and the toughness of the PMMA / ABS in the polyurethane foam composite PMMA / ABS special structural panels is not affected.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a method for preparing a polyurethane foamed composite PMMA / ABS structural plate. Background Art

[0002] PMMA / ABS is a laminate material with excellent properties. Its outer layer is composed of PMMA (polymethyl methacrylate), which has characteristics such as high gloss, UV resistance, scratch resistance, and chemical corrosion resistance; the inner layer is composed of ABS (acrylonitrile-butadiene-styrene copolymer), which has excellent physical and chemical properties such as high strength, high toughness, and impact resistance. The characteristics of this material make it widely used in the appearance and structure of automobiles, including the roof, side panels, doors, and front of the car. However, when using PMMA / ABS special structural panels sold on the market, such as automotive roof forehead products, the top forehead of the car (i.e., PMMA / ABS panels) will crack after a period of use by customers, which is far from the end of its service life, increasing costs for the company.

[0003] Polyurethane foam is an excellent thermal insulation material with excellent thermal and sound insulation properties, as well as good compressive strength and durability. In automobiles, polyurethane foam is often used as an inner filling material, effectively improving the thermal and sound insulation properties of the vehicle interior, while also increasing the vehicle's strength and stability and reducing the vehicle's bumpiness during driving. Combining PMMA / ABS with polyurethane foam can improve thermal insulation and compressive strength, but a series of experimental analyses have found that residual polyurethane raw materials after foaming affect the mechanical properties of PMMA / ABS, resulting in a decrease in the elongation at break of the PMMA / ABS material, which in turn reduces its toughness. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a novel polyurethane foam composite, which can overcome the problem of decreased elongation at break when compounded with PMMA / ABS to produce a laminate material.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A method for preparing a polyurethane foam composite PMMA / ABS structural plate comprises the following steps:

[0007] 1) Preparation of polyol composition A: polyol, chain extender, dicyclopentadiene, blowing agent, catalyst and stabilizer were added into a reaction kettle according to metered amounts and stirred for 30 to 60 minutes at room temperature and pressure to mix uniformly;

[0008] 2) SRIM process: The polyol composition A and the isocyanate component B are drawn into the isocyanate and polyol storage tanks respectively. The two raw materials are measured at a ratio of A:B = 100:150-170, and are delivered to the mixing head through a transportation pipeline. After being mixed evenly, they are sprayed into the mold. A PMMA / ABS sheet is placed on the mold. The mold is closed and pressure maintained for 7 minutes. The raw material temperature is controlled at 25-35°C, and the mold temperature is 50-80°C.

[0009] Furthermore, the polyol composition A comprises the following components in parts by weight:

[0010] 40-65 parts by weight of polyol a1: sorbitol polyether polyol;

[0011] 15 to 25 parts by weight of polyol a2: ethylenediamine polyether tetraol;

[0012] 10 to 20 parts by weight of polyol a3: glycerol polyether polyol;

[0013] 1 to 10 parts by weight of a chain extender and crosslinker a4: a small molecule alcohol crosslinker and chain extender;

[0014] 0.5 to 2 parts by weight of dicyclopentadiene;

[0015] 1-2 parts by weight of a foaming agent: water;

[0016] 0.3 to 1.5 parts by weight of a stabilizer: a silicone stabilizer;

[0017] 0.5 to 1 parts by weight of catalyst b1: an amine catalyst;

[0018] 0.1 to 1 parts by weight of catalyst b2: a tin catalyst.

[0019] Furthermore, the functionality of the polyol a1 is 4-4.5, and the hydroxyl value is 500 mg KOH / g; the functionality of the polyol a2 is 4, and the hydroxyl value is 800 mg KOH / g; and the functionality of the polyol a3 is 3, and the hydroxyl value is 450-500 mg KOH / g.

[0020] Furthermore, the chain extender crosslinker a4 is a small molecule alcohol crosslinker chain extender, selected from one of ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, diethanolamine, and triethanolamine.

[0021] Furthermore, the catalyst b1 is an amine catalyst, selected from any two combinations of N,N-dimethylcyclohexylamine, DMEA, triethanolamine, and triethylenediamine.

[0022] Furthermore, the isocyanate component B is polymethylene polyphenyl polyisocyanate.

[0023] Compared with the prior art, the present invention has the following advantages: It utilizes all-water foaming to produce polyurethane foam for use in polyurethane foam composite PMMA / ABS special structural panels. A certain amount of dicyclopentadiene is added during the preparation process. During the polyurethane foaming process, it migrates to the foam surface to form a film. This film has air-drying properties, a hard, transparent surface, and excellent weather and chemical resistance. It can also block the effects of the polyurethane raw materials on the PMMA / ABS, thereby maintaining the toughness of the PMMA / ABS material and improving its mechanical properties. DETAILED DESCRIPTION

[0024] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0025] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0026] Example

[0027] A method for preparing a polyurethane foam composite PMMA / ABS structural plate comprises the following steps:

[0028] 1) Preparation of polyol composition A: polyol, chain extender, dicyclopentadiene, blowing agent, catalyst and stabilizer were added into a reaction kettle according to metered amounts and stirred for 30 to 60 minutes at room temperature and pressure to mix uniformly;

[0029] 2) SRIM process: The polyol composition A and the isocyanate component B are drawn into the isocyanate and polyol storage tanks respectively. The two raw materials are measured at a ratio of A:B = 100:150-170, and are delivered to the mixing head through a transportation pipeline. After being mixed evenly, they are sprayed into the mold. A PMMA / ABS sheet is placed on the mold. The mold is closed and pressure maintained for 7 minutes. The raw material temperature is controlled at 25-35°C, and the mold temperature is 50-80°C.

[0030] The raw materials and equipment used in the specific embodiments of the present invention are all known products, which are obtained by purchasing commercial products. Among them, the isocyanate component B is Suprasec 5005 from Huntsman.

[0031] Example 1:

[0032] The following components were mixed to obtain a polyol component: 60 parts of polyether 6305B, 15 parts of ethylenediamine polyether tetraol, 10 parts of glycerol polyether polyol, 4 parts of ethylene glycol, 1 part of dicyclopentadiene, 2 parts of water, 1 part of stabilizer (AK8805), 0.3 parts of triethanolamine, 0.2 parts of DMEA, and 0.2 parts of dibutyltin dilaurate were added to a reaction kettle and stirred at room temperature and pressure for 30 to 60 minutes to mix evenly;

[0033] The isocyanate component Suprasec 5005 and the above-mentioned polyol components were pumped into the isocyanate and polyol storage tanks respectively. The two raw materials were measured in a ratio of 160:100 and sent to the mixing head through a transportation pipeline. After being mixed evenly, they were sprayed into the mold. A PMMA / ABS sheet was placed on the mold. The mold was closed and pressure maintained for 7 minutes. The raw material temperature was controlled at 25-35°C and the mold temperature was 50-80°C.

[0034] Example 2

[0035] The following components were mixed to obtain a polyol component: 65 parts of polyether 6305B, 20 parts of ethylenediamine polyether tetraol, 10 parts of glycerol polyether polyol, 4 parts of ethylene glycol, 1.5 parts of dicyclopentadiene, 2 parts of water, 1 part of AK8805, 0.3 parts of triethanolamine, 0.3 parts of DMEA, and 0.2 parts of dibutyltin dilaurate were added to a reaction kettle and stirred at room temperature and pressure for 30 to 60 minutes to mix evenly;

[0036] SRIM process: The isocyanate component Suprasec 5005 and the above-mentioned polyol components are respectively pumped into the isocyanate and polyol storage tanks. The two raw materials are measured in a ratio of 170:100 and sent to the mixing head through a transportation pipeline. After being mixed evenly, they are sprayed into the mold. PMMA / ABS sheet is placed on the mold. The mold is closed and pressure is maintained for 7 minutes. The raw material temperature is controlled at 25-35°C, and the mold temperature is 50-80°C.

[0037] Example 3

[0038] The following components were mixed to obtain a polyol component: 63 parts of polyether 6305B, 14 parts of ethylenediamine polyether tetraol, 8 parts of glycerol polyether polyol, 4 parts of ethylene glycol, 0.5 parts of dicyclopentadiene, 2 parts of water, 1 part of AK8805, 0.25 parts of triethanolamine, 0.25 parts of DMEA, and 0.2 parts of dibutyltin dilaurate were added to a reaction kettle and stirred at room temperature and pressure for 30 to 60 minutes to mix evenly;

[0039] SRIM process: The isocyanate component Suprasec 5005 and the above-mentioned polyol components are respectively pumped into the isocyanate and polyol storage tanks. The two raw materials are measured in a ratio of 150:100 and sent to the mixing head through a transportation pipeline. After being mixed evenly, they are sprayed into the mold. PMMA / ABS sheet is placed on the mold. The mold is closed and pressure is maintained for 7 minutes. The raw material temperature is controlled at 25-35°C, and the mold temperature is 50-80°C.

[0040] Comparative Example 1:

[0041] The raw materials and steps are the same as those in Example 1, wherein the amount of cyclopentadiene is 0.

[0042] Comparative Example 2:

[0043] The raw materials and steps are the same as those in Example 1, wherein the amount of cyclopentadiene is 3 parts.

[0044] The performance test data of the polyurethane foam materials of Examples 1 to 3 and Comparative Examples 1 to 2 are shown in Table 1.

[0045]

[0046] As can be seen from Table 1 by the embodiments and comparative examples, the polyurethane foam that does not add dicyclopentadiene has an impact on the mechanical property of PMMA / ABS sheet material, and especially the elongation at break is disclosed, and i.e. toughness is relatively poor. Dicyclopentadiene can move to the foam surface to form a kind of film in the polyurethane foaming process, and this film has air drying performance, and the surface is hard, transparent, weather-resistant and chemical-resistant, can block the impact of polyurethane raw material on PMMA / ABS, so that the toughness of PMMA / ABS material is well maintained. But adding excessive dicyclopentadiene can cause the decline of the mechanical property of polyurethane foam material.

[0047] In summary, the present invention adopts full water foaming to prepare the polyurethane foam for polyurethane foam composite PMMA / ABS special structural board. The polyurethane foam prepared by the present invention has good mechanical properties, and the toughness of PMMA / ABS in the polyurethane foam composite PMMA / ABS special structural board is not affected.

[0048] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the description and implementation methods. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A method for preparing a polyurethane foam composite PMMA / ABS structural plate, characterized in that: The steps include: 1) Preparation of polyol composition A: Add polyol, chain extender, dicyclopentadiene, blowing agent, catalyst, and stabilizer into a reaction kettle according to metered amounts and stir for 30-60 minutes at room temperature and pressure to mix uniformly; 2) SRIM process: The polyol composition A and the isocyanate component B are pumped into the isocyanate and polyol storage tanks, respectively. The two raw materials are measured at a ratio of A:B = 100:150-170. The two raw materials are delivered to the mixing head through a transportation pipeline. After being mixed evenly, they are sprayed into the mold. A PMMA / ABS sheet is placed on the mold. The mold is closed and pressure-held for 7 minutes. The raw material temperature is controlled at 25-35°C, and the mold temperature is 50-80°C. The polyol composition A comprises the following components in parts by weight: 40-65 parts by weight of polyol a1: sorbitol polyether polyol; 15-25 parts by weight of polyol a2: ethylenediamine polyether tetraol; 10-20 parts by weight of polyol a3: glycerol polyether polyol; 1 to 10 parts by weight of a chain extender and crosslinker a4: a small molecule alcohol crosslinker and chain extender; 0.5-2 parts by weight of dicyclopentadiene; 1-2 parts by weight of a foaming agent: water; 0.3~1.5 parts by weight of stabilizer: silicone stabilizer; 0.5 to 1 parts by weight of catalyst b1: an amine catalyst; 0.1 to 1 parts by weight of catalyst b2: a tin catalyst.

2. The method for preparing the polyurethane foam composite PMMA / ABS structural plate according to claim 1, wherein: The functionality of the polyol a1 is 4-4.5, and the hydroxyl value is 500 mg KOH / g; the functionality of the polyol a2 is 4, and the hydroxyl value is 800 mg KOH / g; the functionality of the polyol a3 is 3, and the hydroxyl value is 450-500 mg KOH / g.

3. The method for preparing the polyurethane foam composite PMMA / ABS structural plate according to claim 1, wherein: The chain extender crosslinker a4 is a small molecule alcohol crosslinker chain extender, selected from one of ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, diethanolamine, and triethanolamine.

4. The method for preparing the polyurethane foam composite PMMA / ABS structural plate according to claim 1, wherein: The catalyst b1 is an amine catalyst, selected from any combination of two of N,N-dimethylcyclohexylamine, DMEA, triethanolamine, and triethylenediamine.

5. The method for preparing the polyurethane foam composite PMMA / ABS structural plate according to claim 1, wherein: The isocyanate component B is polymethylene polyphenyl polyisocyanate.

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