A bio-based polyurethane composite resin composition

Abstract

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

Description

Technical Field

[0001] This invention belongs to the field of composite materials, specifically relating to a bio-based polyurethane composite resin composition and its application in the field of composite materials. Background Technology

[0002] Polyurethane composites are made from polyurethane resin and matrix reinforcement materials through pultrusion, winding, and other methods, and are widely used in various applications requiring lightweight and high strength. The choice of polyurethane resin has a significant impact on the strength, weather resistance, and processing conditions of polyurethane composites. Currently, few polyurethane resins simultaneously possess low viscosity, high weather resistance, and excellent mechanical properties. Summary of the Invention

[0003] The purpose of this invention is to provide a bio-based polyurethane composite resin composition that, based on a specific isocyanate, simultaneously possesses characteristics such as low viscosity, ease of processing, high strength, and good weather resistance.

[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] Component A is a polyisocyanate component, which contains 40-70 wt% of 1,3-phenylenedimethylene diisocyanate and 30-60 wt% of 1,5-pentanediisocyanate prepolymer.

[0007] Component B is a polyether polyol composition containing one or more polyether polyols and a catalyst, wherein the hydroxyl value of the polyether polyol is 150-350 mg KOH / g.

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

[0009] The heating reaction temperature is 50–100℃, preferably 60–80℃;

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

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

[0012] The catalyst is one or more of organotin salts and organobismuth salts, preferably one or more of dibutyltin dilaurate, tin isooctanoate, and bismuth isooctanoate, more preferably dibutyltin dilaurate;

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

[0014] In this 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 components of automobiles and buildings, and can be used by pultrusion molding, filament winding molding, hand lay-up molding, injection molding or a combination thereof.

[0016] The beneficial effects of this invention are as follows:

[0017] The bio-based polyurethane composite composition of this invention innovatively employs a combination of 1,3-phenylenediamine diisocyanate and 1,5-pentanediisocyanate prepolymers. Surprisingly, due to the unique five-carbon molecular structure of the bio-based product 1,5-pentanediisocyanate, it exhibits significantly lower viscosity compared to conventional prepolymers of the same degree of polymerization, resulting in a longer gel time and extended working life. Prepolymerization with pentaerythritol effectively enhances the crosslinking degree of the product, thus achieving a balance between low viscosity and high mechanical properties. Simultaneously, the combination with 1,3-phenylenediamine diisocyanate effectively improves product strength and provides good weather resistance. This composition unexpectedly achieves excellent comprehensive performance in terms of processability, weather resistance, and strength. Detailed Implementation

[0018] To illustrate the effects of the present invention, embodiments are provided for further detailed explanation, but the present invention is not limited to these embodiments.

[0019] The raw materials used in the examples are from the following sources:

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

[0021] PDI, manufactured by Wanhua Chemical Group Co., Ltd., is marketed under the name WANNATE BIO PDI.

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

[0023] HDI, manufactured by Wanhua Chemical Group Co., Ltd., is marketed under the name WANNATE HDI.

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

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

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

[0027] PPG1000 was purchased from Lanxing Dongda, and its product name is DL-1000D (polypropylene glycol, molecular weight 1000).

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

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

[0030] Test method:

[0031] Gel time: Record the time from mixing the polyurethane composition to the start of gelation, at an ambient temperature of 25°C and an ambient humidity of 30-50% RH.

[0032] Weather resistance test: Perform 2000h accelerated aging test according to the Q-SUN test conditions in ASTM D904-99.

[0033] Example 1

[0034] Preparation of 1,5-pentanediisocyanate prepolymer: 1000g PDI and 200g pentaerythritol were added to the reactor and reacted under heating conditions at 60℃. The NCO content was monitored during the process until the NCO content reached the reaction endpoint of about 24.4%. The mixture was then cooled to room temperature for later use. The viscosity of the prepolymer at 25℃ was measured to be 1200cps.

[0035] Preparation of resin composition:

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

[0037] Polyether polyol components: 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] In application, glass fibers are uniformly cut into short glass fibers with a length of 25mm to 30mm and mixed with resin composition at a mass ratio of 4:1. The mixture is then placed in a mold, pressurized and heated for curing. The pressure is 80 tons, the heating temperature is 180℃, and the heating time is 5 minutes. After demolding, polyurethane composite material is obtained. The performance is tested, and the results are shown in Table 1.

[0040] Example 2

[0041] Preparation of 1,5-pentanediisocyanate prepolymer: 1000g PDI and 300g pentaerythritol were added to the reactor and reacted under heating conditions at 80℃. The NCO content was monitored during the process until the NCO content reached about 13.0% at the reaction endpoint. The mixture was then cooled to room temperature for later use. The viscosity of the prepolymer at 25℃ was measured to be 1860cps.

[0042] Preparation of resin composition:

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

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

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

[0046] In application, glass fibers are uniformly cut into short glass fibers with a length of 25mm to 30mm and mixed with resin composition at a mass ratio of 4:1. The mixture is then placed in a mold, pressurized and heated for curing. The pressure is 80 tons, the heating temperature is 180℃, and the heating time is 5 minutes. After demolding, polyurethane composite material is obtained. The performance is tested, and the results are shown in Table 1.

[0047] Example 3

[0048] Preparation of 1,5-pentanediisocyanate prepolymer: 1000g PDI and 160g pentaerythritol were added to the reactor and reacted under heating conditions at 70℃. The NCO content was monitored during the process until the NCO content reached the reaction endpoint of about 29.5%. The mixture was then cooled to room temperature for later use. The viscosity of the prepolymer at 25℃ was measured to be 550cps.

[0049] Preparation of resin composition:

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

[0051] Polyether polyol components: Mix 700g MN-500, 600g MN-1000, 200g DL-1000D with 0.4g dibutyltin dilaurate until homogeneous;

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

[0053] In application, glass fibers are uniformly cut into short glass fibers with a length of 25mm to 30mm and mixed with resin composition at a mass ratio of 4:1. The mixture is then placed in a mold, pressurized and heated for curing. The pressure is 80 tons, the heating temperature is 180℃, and the heating time is 5 minutes. After demolding, polyurethane composite material is obtained. The performance is tested, and the results are shown in Table 1.

[0054] Comparative Example 1

[0055] The composition was prepared by referring to the method of Example 1, except that the 1,5-pentanediisocyanate prepolymer was replaced with HT-100 with an equal molar amount of -NCO and the viscosity of HT-100 was 2500 cps. All other operations and parameters were the same as in Example 1.

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

[0057] Comparative Example 2

[0058] The composition was prepared by referring to the method of Example 1, except that XDI was replaced with an equimolar amount of MDI-100, and all other operations and parameters were the same as in Example 1.

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

[0060] Comparative Example 3

[0061] The method of Example 1 was followed, except that 1,5-pentanediisocyanate was replaced with hexamethylene diisocyanate (HDI) to obtain a prepolymer with a viscosity of 3300 cps, and the composition was prepared according to the method of Example 1.

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

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

[0064]

[0065]

Claims

1. A bio-based polyurethane composite resin composition, said composition comprising a) A polyisocyanate component, wherein the polyisocyanate component comprises 40-70 wt% of 1,3-phenylenediethylene diisocyanate and 30-60 wt% of 1,5-pentanediisocyanate prepolymer; wherein... The 1,5-pentanediisocyanate prepolymer is prepared by reacting 1,5-pentanediisocyanate with pentaerythritol. b) Polyether polyol composition.

2. The resin composition according to claim 1, characterized in that, The reaction temperature of 1,5-pentanediisocyanate with pentaerythritol is 50–100 °C.

3. The resin composition according to claim 1, characterized in that, The 1,5-pentanediisocyanate prepolymer has an NCO content of 13%-30%.

4. The resin composition according to claim 1, characterized in that, The viscosity of the 1,5-pentanediisocyanate prepolymer at 25°C is 500-2000 cps.

5. The resin composition according to claim 1, characterized in that, The polyether polyol composition comprises one or more polyether polyols and a catalyst, with a hydroxyl value of 150-350 mg KOH / g.

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

2.

7. The resin composition according to claim 5, characterized in that, The catalyst is one or more of organotin salts and organobismuth salts.

8. The resin composition according to claim 7, characterized in that, The catalyst is one or more of dibutyltin dilaurate, tin isooctanoate, and bismuth isooctanoate.

9. The resin composition according to claim 7, characterized in that, The amount of catalyst used is 0.01%-0.03% of the weight of the polyether polyol composition.

10. The resin composition according to any one of claims 1-9, characterized in that, The resin composition has an isocyanate index of 1.0-1.5.

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