Bio-based polyurethane composite resin composition

Abstract

The present invention relates to a bio-based polyurethane composite material resin composition, which comprises: (1) a polyisocyanate component, which comprises 40-70 wt% of 1, 3-xylylene diisocyanate and 30-60 wt% of a 1, 5-pentamethylene diisocyanate prepolymer, (2) a polyisocyanate component, (3) a polyurethane component, and (4) a polyurethane component, and (2) the polyether polyol composition comprises one or more polyether polyols and a catalyst, the hydroxyl value of the polyether polyols is 150-350 mgKOH / g, and the average functionality of the polyether polyols is 2.8-3.2. The invention also relates to a polyurethane composite material containing the polyurethane resin composition and a reinforcing material.

Description

Technical Field

[0001] The present invention belongs to the field of composite materials, and in particular relates to a bio-based polyurethane composite resin composition and application thereof in the field of composite materials. Background Art

[0002] Polyurethane composite materials are made of polyurethane resin and matrix reinforcement materials through pultrusion, winding and other methods, and are widely used in various lightweight and high-strength applications. The selection of polyurethane resin has a great influence on the strength, weather resistance and processing conditions of polyurethane composite materials. Currently, there are few polyurethane resins that have both low viscosity and high weather resistance and excellent mechanical properties. Summary of the invention

[0003] The object of the present invention is to provide a bio-based polyurethane composite resin composition, which is based on a specific isocyanate and has the characteristics of low viscosity, easy processing, high strength, good weather resistance, etc.

[0004] The technical solution of the present invention is as follows:

[0005] A bio-based polyurethane composite resin composition, the composition comprising two components A and B; wherein:

[0006] The component A is a polyisocyanate component, which contains 40-70 wt% of 1,3-xylylene diisocyanate and 30-60 wt% of 1,5-pentane diisocyanate prepolymer;

[0007] The component B is a polyether polyol composition, comprising one or more polyether polyols and a catalyst, wherein the hydroxyl value of the polyether polyol is 150-350 mgKOH / g.

[0008] In the present invention, in component A, the 1,5-pentane diisocyanate prepolymer is prepared by reacting 1,5-pentane diisocyanate with pentaerythritol under heating conditions, and the NCO content is 13%-30%;

[0009] Wherein, the heating reaction temperature is 50-100°C, preferably 60-80°C;

[0010] Preferably, the viscosity of the 1,5-pentamethylene diisocyanate prepolymer at 25° C. is 500-2000 cps.

[0011] In the present invention, in component B, the average functionality of the polyether polyol is 2.8-3.2;

[0012] The catalyst is one or more of an organic tin salt and an organic bismuth salt, preferably one or more of dibutyltin dilaurate, tin isooctanoate, and bismuth isooctanoate, more preferably dibutyltin dilaurate;

[0013] Preferably, the amount of the catalyst used is 0.01%-0.03% by weight of the polyether polyol composition.

[0014] In the present invention, the bio-based polyurethane composite resin composition has an isocyanate index of 1.0-1.5.

[0015] The bio-based polyurethane composite resin composition of the present invention can be applied to solar panel frames, door and window frames, bathtubs, decorative parts and structural parts of automobiles and buildings, and the use method includes pultrusion molding process, winding molding process, hand lay-up molding process, injection molding process or a combination thereof.

[0016] The beneficial effects of the present invention are:

[0017] The bio-based polyurethane composite composition of the present invention innovatively uses a combination of 1,3-xylylene diisocyanate and 1,5-pentylene diisocyanate prepolymer. Surprisingly, because the bio-based product 1,5-pentylene diisocyanate has a special molecular structure of five carbon atoms, it has a significant low viscosity effect compared to conventional prepolymers of the same degree of polymerization, has a longer gel time, and extends the operating period. After prepolymerization with pentaerythritol, it can effectively improve the cross-linking degree of the product, thereby achieving both low viscosity and high mechanical properties. At the same time, the combination with 1,3-xylylene diisocyanate effectively improves the strength of the product and has good weather resistance. The composition unexpectedly obtains excellent comprehensive performance of processing, weather resistance and strength. DETAILED DESCRIPTION

[0018] In order to illustrate the effects of the present invention, the present invention is further described in detail with reference to examples, but the present invention is not limited to these examples.

[0019] The sources of the raw materials used in the examples are as follows:

[0020] XDI, Wanhua Chemical Group Co., Ltd., trade name WANNATE X-500;

[0021] PDI, Wanhua Chemical Group Co., Ltd., trade name WANNATE BIO PDI;

[0022] MDI, Wanhua Chemical Group Co., Ltd., trade name WANNATE MDI-100;

[0023] HDI, Wanhua Chemical Group Co., Ltd., trade name WANNATE HDI

[0024] HDI trimer, Wanhua Chemical Group Co., Ltd., trade name WANNATE HT-100

[0025] MN-500 was purchased from Bluestar Dongda (polyoxypropylene triol, molecular weight 500);

[0026] MN-1000 was purchased from Bluestar Dongda (polyoxypropylene triol, molecular weight 1000);

[0027] PPG1000 was purchased from Bluestar Dongda under the trade name DL-1000D (polypropylene glycol, molecular weight 1000);

[0028] WANOL S3007, Wanhua Chemical Group Co., Ltd. (polyoxypropylene triol, molecular weight 700);

[0029] Unless otherwise specified, other reagents are commercially available.

[0030] Test method:

[0031] Gel time: record the time from the time the polyurethane composition is mixed to the time the composition begins to gel, the ambient temperature is 25°C, the ambient humidity is 30-50% RH

[0032] Weathering test: Refer to the Q-SUN test conditions in ASTM D904-99 and complete 2000h artificial accelerated aging test.

[0033] Example 1

[0034] Preparation of 1,5-pentanediisocyanate prepolymer: 1000 g PDI and 200 g pentaerythritol were added to the reactor and reacted at 60°C. The NCO content was monitored during the process until the NCO content reached 24.4% near the end point of the reaction, and then dropped to room temperature for use. The viscosity of the prepolymer was measured to be 1200 cps at 25°C.

[0035] Preparation of resin composition:

[0036] Polyisocyanate component: Take 500g of the above 1,5-pentanediisocyanate prepolymer and 500g of XDI and stir them evenly at room temperature;

[0037] Polyether polyol component: Mix 600g MN-500, 600g S3007 and 0.15g dibutyltin dilaurate evenly;

[0038] The isocyanate index of the above resin composition is 1.3;

[0039] When used, the glass fiber is uniformly cut into short glass fibers with a length of 25 mm to 30 mm, mixed with the resin composition in a mass ratio of 4:1, and placed in a mold for pressurized heating and curing. The pressure is 80 tons, the heating temperature is 180°C, and the heating time is 5 minutes. The polyurethane composite material is demoulded to obtain the performance test. The results are shown in Table 1.

[0040] Example 2

[0041] Preparation of 1,5-pentanediisocyanate prepolymer: 1000 g PDI and 300 g pentaerythritol were added to a reactor and reacted at 80° C. The NCO content was monitored during the process until the NCO content reached 13.0% near the end point of the reaction, then dropped to room temperature for use. The viscosity of the prepolymer was measured to be 1860 cps at 25° C.

[0042] Preparation of resin composition:

[0043] Polyisocyanate component: 600 g of the above-mentioned 1,5-pentanediisocyanate prepolymer and 400 g of XDI were stirred evenly at room temperature;

[0044] Polyether polyol component: 800g MN-500, 200g S3007 and 0.2g bismuth isooctanoate were mixed evenly;

[0045] The isocyanate index of the resin composition is 1.08.

[0046] When used, the glass fiber is uniformly cut into short glass fibers with a length of 25 mm to 30 mm and mixed with the resin composition in a mass ratio of 4:1 and placed in a mold. The mixture is pressurized and heated for curing. The pressure is 80 tons, the heating temperature is 180°C, and the heating time is 5 minutes. The polyurethane composite material is demoulded to obtain the polyurethane composite material. The performance is tested. The results are shown in Table 1.

[0047] Example 3

[0048] Preparation of 1,5-pentanediisocyanate prepolymer: 1000 g PDI and 160 g pentaerythritol were added to the reactor and reacted at 70° C. The NCO content was monitored during the process until the NCO content reached 29.5% near the end point of the reaction, then dropped to room temperature for use. The viscosity of the prepolymer was measured to be 550 cps at 25° C.

[0049] Preparation of resin composition:

[0050] Polyisocyanate component: 300 g of the above-mentioned 1,5-pentanediisocyanate prepolymer and 700 g of XDI were stirred evenly at room temperature;

[0051] Polyether polyol component: Take 700g MN-500, 600g MN-1000, 200g DL-1000D and 0.4g dibutyltin dilaurate and mix them evenly;

[0052] The isocyanate index of the resin composition is 1.45.

[0053] When used, the glass fiber is uniformly cut into short glass fibers with a length of 25 mm to 30 mm and mixed with the resin composition in a mass ratio of 4:1 and placed in a mold. The mixture is pressurized and heated for curing. The pressure is 80 tons, the heating temperature is 180°C, and the heating time is 5 minutes. The polyurethane composite material is demoulded to obtain the polyurethane composite material. The performance is tested. The results are shown in Table 1.

[0054] Comparative Example 1

[0055] The method of Example 1 was referred to, except that the 1,5-pentane diisocyanate prepolymer was replaced with HT-100 with an equal molar amount of -NCO, and the viscosity of HT-100 was 2500 cps. Other operations and parameters were the same as those of Example 1 to prepare a composition.

[0056] The above composition was used according to the method of Example 1 to prepare a polyurethane composite sample, and its performance was tested after curing. The results are shown in Table 1.

[0057] Comparative Example 2

[0058] The method of Example 1 was referred to, except that XDI was replaced by an equal molar amount of MDI-100, and other operations and parameters were the same as those of Example 1 to prepare a composition.

[0059] The above composition was used according to the method of Example 1 to prepare a polyurethane composite sample, and its performance was tested after curing. The results are shown in Table 1.

[0060] Comparative Example 3

[0061] The method of Example 1 is referred to, except that: according to the same -NCO content of the prepolymer, 1,5-pentane diisocyanate is replaced with hexamethylene diisocyanate (HDI) to obtain a prepolymer with a viscosity of 3300 cps, and a composition is prepared according to the method of Example 1.

[0062] The above composition was used according to the method of Example 1 to prepare a polyurethane composite sample, and its performance was tested after curing. The results are shown in Table 1.

[0063] Table 1 Performance test results of embodiments and comparative examples

[0064]

[0065]

Claims

1. A bio-based polyurethane composite resin composition, the composition comprising a) a polyisocyanate component, wherein the polyisocyanate component comprises 40-70 wt % of 1,3-xylylene diisocyanate and 30-60 wt % of 1,5-pentamethylene diisocyanate prepolymer; b) Polyether polyol compositions.

2. The resin composition according to claim 1, characterized in that The 1,5-pentamethylene diisocyanate prepolymer is prepared by reacting 1,5-pentamethylene diisocyanate with pentaerythritol; preferably, the reaction temperature is 50-100°C.

3. The resin composition according to any one of claims 1 to 2, characterized in that The NCO content of the 1,5-pentamethylene diisocyanate prepolymer is 13%-30%.

4. The resin composition according to any one of claims 1 to 3, characterized in that The viscosity of the 1,5-pentamethylene diisocyanate prepolymer at 25° C. is 500-2000 cps.

5. The resin composition according to any one of claims 1 to 4, characterized in that The polyether polyol composition comprises one or more polyether polyols and a catalyst, and has a hydroxyl value of 150-350 mgKOH / g.

6. The resin composition according to any one of claims 1 to 5, characterized in that The average functionality of the polyether polyol is 2.8-3.

2.

7. The resin composition according to any one of claims 5 to 6, characterized in that The catalyst is one or more of organic tin salts and organic bismuth salts, preferably one or more of dibutyltin dilaurate, tin isooctanoate, and bismuth isooctanoate; preferably, the amount of the catalyst is 0.01%-0.03% by weight of the polyether polyol composition.

8. The resin composition according to any one of claims 1 to 7, characterized in that The resin composition has an isocyanate index of 1.0-1.5.

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