Vinyl ester resin for pultrusion and preparation method thereof

Abstract

The invention discloses vinyl ester resin for pultrusion and a preparation method thereof, and relates to the technical field of resin preparation, 400-500 g of epoxy resin E51 is added into a flask, the temperature is raised to 110 DEG C, 0.20 g of a polymerization inhibitor methylhydroquinone is added, 10-200 g of methacrylic acid starts to be dropwise added, and the temperature is kept at 110-115 DEG C for reaction; then 10-50 g of polycarbonate glycol is added, and the mixture is stirred to be uniform; then adding 10-50g of diphenylmethane diisocyanate (MDI), and continuously reacting for half an hour; and cooling the reactant to below 95 DEG C, adding 300-1000g of metered styrene, and uniformly mixing to obtain the epoxy vinyl ester resin for pultrusion. The carbamate and the polycarbonate diol are introduced, so that the weather resistance and the flexibility of the resin can be effectively improved.

Description

Technical Field

[0001] The invention relates to the technical field of resin preparation, and in particular to a vinyl ester resin for pultrusion and a preparation method thereof. Background Art

[0002] Vinyl ester resin has excellent reactivity, but it lacks in weather resistance and flexibility compared to polyurethane resin. Summary of the invention

[0003] The purpose of the present invention is to address the defects and shortcomings of the prior art and provide a vinyl ester resin for pultrusion and a preparation method thereof. The introduction of carbamate and polycarbonate diol can effectively improve the weather resistance and flexibility of the resin.

[0004] To achieve the above-mentioned purpose, the present invention adopts the following technical scheme: the vinyl ester resin for pultrusion of the present invention comprises the following components by weight: 400-500g of epoxy resin, 10-200g of methacrylic acid, 10-50g of diphenylmethane diisocyanate (MDI), 10-50g of polycarbonate diol and 300-1000g of styrene.

[0005] Preferably, the vinyl ester resin for pultrusion comprises the following components by weight: 450 g of epoxy resin, 80 g of methacrylic acid, 30 g of diphenylmethane diisocyanate (MDI), 20 g of polycarbonate diol and 400 g of styrene.

[0006] Preferably, the base epoxy resin is base epoxy resin E51 or E44.

[0007] Preferably, the diphenylmethane diisocyanate (MDI) is pure MDI or polymeric MDI.

[0008] Preferably, the number average molecular weight of the polycarbonate diol is 800-3000 g / mol.

[0009] The method for preparing an epoxy vinyl ester resin for pultrusion according to the present invention comprises the following steps: Step 1, add 400-500g of epoxy resin E51 into a flask, heat to 110°C, add 0.20g of polymerization inhibitor methyl hydroquinone, start to drop 10-200g of methacrylic acid, and keep the reaction at 110-115°C; Step 2, add 10-50g of polycarbonate diol and stir evenly; Step 3, add 10-50g of diphenylmethane diisocyanate (MDI) and continue the reaction for half an hour; Step 4: Cool the reactants to below 95° C., add 300-1000 g of styrene, and mix well to obtain epoxy vinyl ester resin for pultrusion.

[0010] Preferably, the acid value tested during the control process in step 1 is ≤10 mgKOH / g.

[0011] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention provides a vinyl ester resin for pultrusion and a preparation method thereof, wherein epoxy resin and monobasic unsaturated carboxylic acid are reacted to synthesize epoxy vinyl ester resin, and when the reaction reaches a certain acid value, polycarbonate diol and diphenylmethane diisocyanate (MDI) are added to introduce carbamate and carbonate structures, and when the end point is reached, a suitable amount of styrene is added for dilution, which can effectively improve the weather resistance and flexibility of the resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 This is a performance comparison table of Example 1, Example 2, Example 3 and existing vinyl ester resin. DETAILED DESCRIPTION

[0013] The technical solution of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. The preferred embodiments in the description are only used as examples, and all other embodiments obtained by those skilled in the art without making any creative work are within the scope of protection of the present invention.

[0014] Embodiment 1: This embodiment adopts the following technical scheme: it comprises the following components by weight: epoxy resin E51400g, methacrylic acid 50g, polymerized MDI 15g, polycarbonate glycol 20g, styrene 400g, catalyst benzyltriethylammonium chloride 3.08g, and inhibitor methylhydroquinone 0.20g.

[0015] The preparation method of this embodiment is as follows: Step 1, add 400g of epoxy resin E44 into a flask, heat to 110°C, add 0.20g of methyl hydroquinone as polymerization inhibitor, start to drop 50g of methacrylic acid, keep the reaction at 110-115°C, and test the acid value ≤10mgKOH∕g during the control process; Step 2, add 20g of polycarbonate diol (molecular weight 900) and stir evenly; Step 3, add 30g of polymeric MDI and continue the reaction for half an hour; Step 4: Then cool the reactants to below 95° C., add 400 g of styrene in a measured amount, and mix well to obtain epoxy vinyl ester resin for pultrusion.

[0016] Embodiment 2: This embodiment adopts the following technical scheme: it comprises the following components by weight: epoxy resin E51450g, methacrylic acid 60g, pure MDI 35g, polycarbonate diol (molecular weight 2000) 10g, styrene 600g, catalyst benzyltriethylammonium chloride 3.08g, inhibitor methylhydroquinone 0.20g.

[0017] The preparation method of this embodiment is as follows: Step 1, add 450g of epoxy resin E51 into a flask, heat to 110°C, add 0.20g of methyl hydroquinone as polymerization inhibitor, start to drop 60g of methacrylic acid, keep the reaction at 110-115°C, and test the acid value ≤10mgKOH∕g during the control process; Step 2, add 10g of polycarbonate diol and stir evenly; Step 3, add 35g of diphenylmethane diisocyanate (MDI) and continue the reaction for half an hour; Step 4: Then cool the reactants to below 95° C., add 600 g of styrene in a measured amount, and mix well to obtain epoxy vinyl ester resin for pultrusion.

[0018] Embodiment 3: This embodiment adopts the following technical scheme: it comprises the following components by weight: epoxy resin E51500g, methacrylic acid 100g, pure MDI 50g, polycarbonate diol (molecular weight 2000) 50g, styrene 1000g, catalyst benzyltriethylammonium chloride 3.08g, and inhibitor methylhydroquinone 0.20g.

[0019] The preparation method of this embodiment is as follows: Step 1, add 500g of epoxy resin E51 into a flask, heat to 110°C, add 0.20g of polymerization inhibitor methyl hydroquinone, start to drop 100g of methacrylic acid, keep the reaction at 110-115°C, and test the acid value ≤10mgKOH∕g during the control process; Step 2, add 50g of polycarbonate diol and stir evenly; Step 3, add 50 g of diphenylmethane diisocyanate (MDI) and continue the reaction for half an hour; Step 4: Then cool the reactants to below 95° C., add 1000 g of styrene, and mix well to obtain epoxy vinyl ester resin for pultrusion.

[0020] Experimental comparison: The above-mentioned embodiment 1, embodiment 2, embodiment 3 and the existing vinyl ester resin were tested and compared in performance, see Figure 1 ,from Figure 1It can be seen that the vinyl ester resin for pultrusion prepared by the first and second embodiments is superior to the existing vinyl ester resin in terms of tensile strength, elongation at break, 200h color difference and 1000h color difference.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention provides a vinyl ester resin for pultrusion and a preparation method thereof, wherein epoxy resin and monobasic unsaturated carboxylic acid are reacted to synthesize epoxy vinyl ester resin, and when the reaction reaches a certain acid value, polycarbonate diol and diphenylmethane diisocyanate (MDI) are added to introduce carbamate and carbonate structures, and when the end point is reached, a suitable amount of styrene is added for dilution, which can effectively improve the weather resistance and flexibility of the resin.

[0022] For those skilled in the art, they can modify the technical solutions described in the aforementioned embodiments and make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A vinyl ester resin for pultrusion, characterized in that: It contains the following components by weight: 400-500g of epoxy resin, 10-200g of methacrylic acid, 10-50g of diphenylmethane diisocyanate, 10-50g of polycarbonate diol and 300-1000g of styrene.

2. A vinyl ester resin for pultrusion according to claim 1, characterized in that: The vinyl ester resin for pultrusion comprises the following components by weight: 450 g of epoxy resin, 80 g of methacrylic acid, 30 g of diphenylmethane diisocyanate, 20 g of polycarbonate diol and 400 g of styrene.

3. A vinyl ester resin for pultrusion according to claim 2, characterized in that: The base epoxy resin is base epoxy resin E51 or E44.

4. A vinyl ester resin for pultrusion according to claim 3, characterized in that: The diphenylmethane diisocyanate is pure MDI or polymerized MDI.

5. A vinyl ester resin for pultrusion according to claim 4, characterized in that: The number average molecular weight of the polycarbonate diol is 800-3000 g / mol.

6. A method for preparing epoxy vinyl ester resin for pultrusion, comprising the following steps: Step (1), add 400-500g of epoxy resin E51 into a flask, raise the temperature to 110°C, add 0.20g of methyl hydroquinone as a polymerization inhibitor, start to dropwise add 10-200g of methacrylic acid, and keep the reaction at 110-115°C; Step (2), add 10-50g of polycarbonate diol and stir evenly; Step (3), add 10-50 g of diphenylmethane diisocyanate and continue the reaction for half an hour; Step (4), cooling the reactants to below 95° C., adding 300-1000 g of styrene in a measured amount, and mixing well to obtain epoxy vinyl ester resin for pultrusion.

7. The method for preparing a vinyl ester resin for pultrusion according to claim 6, characterized in that: In the control process of step (1), the acid value is tested to be ≤10 mgKOH / g.

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