Silicone hyperbranched epoxy resin for photocuring 3D printing, preparation method and application thereof on photosensitive resin

Abstract

The present invention relates to an organosilicon hyperbranched epoxy resin for photocuring 3D printing, a preparation method and its application on a photosensitive resin. The present invention is used for the preparation method of the organosilicon hyperbranched epoxy resin for photocuring 3D printing, comprising the following steps: adding a silane coupling agent with an alicyclic epoxy group, a polyether polyol and a catalyst I to a reactor, reacting for 2-48h under 40-120°C, and removing by-products by rotary evaporation; then adding bisphenol A epoxy resin and catalyst II, reacting for 2-12h under 50-150°C, and obtaining the organosilicon hyperbranched epoxy resin for photocuring 3D printing. The present invention balances the strength, toughness and photoreactivity of the epoxy resin prepared by the organosilicon hyperbranched epoxy resin, so that the photosensitive resin prepared by the organosilicon hyperbranched epoxy resin of the present invention can greatly improve the toughness while the strength does not decay.

Description

Technical Field

[0001] The present invention relates to the field of photocuring 3D printing, and in particular to an organosilicon hyperbranched epoxy resin for photocuring 3D printing and a preparation method thereof. Background Art

[0002] At present, the epoxy resins for photocuring 3D printing mainly use alicyclic epoxy and bisphenol A epoxy resins. The traditional alicyclic epoxy and bisphenol A epoxy resins lack flexible segments, which makes the cured products brittle. Hyperbranched epoxy resins have low viscosity, high functionality, and many flexible groups, which significantly improve the strength and toughness of epoxy resins. However, the active groups of traditional hyperbranched epoxy resins are aliphatic glycidyl ethers, which react slowly with cations during the photocuring process and are not suitable for photocuring 3D printing. Silicone polymers have the characteristics of low viscosity, low water absorption, and high flexibility, and have obvious toughening effects, but they are not compatible with epoxy resins, and the mixture is prone to phase separation and strength attenuation.

[0003] Therefore, how to utilize the flexibility of silicone in molecular structure while improving the reactivity of hyperbranched epoxy to strengthen and toughen photocurable resin is an urgent problem to be solved in the industry. Summary of the invention

[0004] The object of the present invention is to provide an organosilicon hyperbranched epoxy resin for photocuring 3D printing, a preparation method and its application in photosensitive resin, specifically including an organosilicon hyperbranched epoxy resin for photocuring 3D printing, a preparation method thereof, a photosensitive resin prepared from the organosilicon hyperbranched epoxy resin and a preparation method thereof. The present invention balances the strength, toughness and photoreactivity of the prepared epoxy resin by using the organosilicon hyperbranched epoxy resin, so that the photosensitive resin prepared by using the organosilicon hyperbranched epoxy resin of the present invention can greatly improve the toughness while not attenuating the strength.

[0005] The present invention is achieved through the following technical solutions:

[0006] Solution 1)

[0007] A method for preparing a silicone hyperbranched epoxy resin for photocuring 3D printing comprises the following steps:

[0008] Add a silane coupling agent with alicyclic epoxy groups, polyether polyol and catalyst I into a reactor, react at 40-120° C. for 2-48 hours, and remove by-products by rotary evaporation;

[0009] Then, bisphenol A epoxy resin and catalyst II are added, and the mixture is reacted at 50-150° C. for 2-12 hours to obtain the organosilicon hyperbranched epoxy resin for photocuring 3D printing;

[0010] The catalyst I is a basic catalyst, and the catalyst II is an imidazole catalyst.

[0011] Specifically, the silane coupling agent with alicyclic epoxy groups is one of 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, or a mixture of the two in any proportion.

[0012] Specifically, the polyol is one or a mixture of any proportion of two or more of glycerol, trimethylolpropane, pentaerythritol, xylitol or sorbitol.

[0013] Specifically, the catalyst I is one of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide or tetraethylammonium hydroxide, or a mixture of two or more of them in any proportion.

[0014] Specifically, the bisphenol A epoxy resin is one of E55, E51, E44, E42, E35, and E20, or a mixture of two or more of them in any proportion.

[0015] Specifically, the catalyst II is one of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole, or a mixture of two or more of them in any proportion.

[0016] Specifically, the mass ratio of alicyclic epoxy group silane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is 100: 68-132: 0.03-0.4: 506-1458: 0.03-0.4.

[0017] Option 2)

[0018] An organosilicon hyperbranched epoxy resin for photocuring 3D printing is prepared by the method described.

[0019] Option 3)

[0020] Application of organosilicon hyperbranched epoxy resin for photocuring 3D printing to prepare photosensitive resin

[0021] Option 4)

[0022] The photosensitive resin includes the organosilicon hyperbranched epoxy resin for photocuring 3D printing.

[0023] The photosensitive resin is prepared from the following components in parts by weight:

[0024]

[0025] The preparation method of the photosensitive resin comprises the following steps:

[0026] First, the photoinitiator TPO, diphenyliodonium hexafluorophosphate, 3-hydroxyoxetane and trimethylolpropane triacrylate are fully dissolved at 55-65°C to obtain a photosensitive diluent.

[0027] Then, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and the organosilicon hyperbranched epoxy resin for photocurable 3D printing are heated and stirred at 140-160° C.; then, after cooling to 75-85° C., the mixture is fully stirred with the photosensitive diluent to obtain the photosensitive resin.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The organosilicon hyperbranched epoxy resin in the present invention has a highly branched structure, high molecular weight, high functionality, and high crosslinking density, and can significantly improve the strength and toughness of the epoxy resin. The photosensitive resin prepared using the organosilicon hyperbranched epoxy resin of the present invention can greatly improve the toughness while not attenuating the strength.

[0030] 2. The organosilicon and polyether structures of the organosilicon hyperbranched epoxy resin in the present invention have high flexibility, while the aromatic glycidyl ether structure has high rigidity, thus ensuring that the toughness is improved while the strength is not reduced.

[0031] 3. The epoxy functional groups of the organosilicon hyperbranched epoxy resin in the present invention are alicyclic epoxy and aromatic glycidyl ether. Compared with traditional aliphatic glycidyl ether, it can react quickly with cations during the photocuring process and has a high degree of reaction, so it is suitable for toughening photocurable 3D printing resins. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is a schematic diagram of the structure of organosilicon hyperbranched epoxy resin;

[0033] Figure 2 is a schematic diagram of an organosilicon coupling agent;

[0034] Figure 3 is a schematic diagram of a polyether polyol;

[0035] Figure 4 This is a schematic diagram of bisphenol A epoxy. DETAILED DESCRIPTION

[0036] The present invention is further described below in conjunction with specific embodiments.

[0037] The present invention provides a method for preparing an organosilicon hyperbranched epoxy resin for photocuring 3D printing, comprising the following steps:

[0038] A silane coupling agent with an alicyclic epoxy group (such as Figure 2 As shown), polyether polyols (such as Figure 3 As shown) and catalyst I are added to the reactor, reacted at 40-120°C for 2-48h, and the by-products are removed by rotary evaporation;

[0039] Then add bisphenol A epoxy resin (such as Figure 4 As shown) and catalyst II, react at 50-150°C for 2-12h to obtain the organosilicon hyperbranched epoxy resin for photocuring 3D printing (as shown) Figure 1 shown).

[0040] A silane coupling agent with alicyclic epoxy groups having strong cationic reactivity reacts with a polyether polyol to form a hyperbranched polyol with epoxy groups, which is further reacted with a bisphenol A epoxy resin to synthesize a hyperbranched silicone epoxy with both alicyclic epoxy groups and aromatic glycidyl ethers.

[0041] The organosilicon hyperbranched epoxy resin of the present invention has a highly branched structure, high molecular weight, high functionality, and high cross-linking density, and can significantly improve the strength and toughness of the epoxy resin.

[0042] Compared with conventional hyperbranched epoxies, the organosilicon hyperbranched epoxy resin in the present invention has the characteristics of rapid curing and high reaction degree, greatly improves toughness while not attenuating strength, and solves the problem of insufficient toughness of traditional photosensitive resins.

[0043] In one embodiment, the silane coupling agent with alicyclic epoxy groups is 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, or a mixture of the two in any proportion.

[0044] In one embodiment, the polyol is one or a mixture of any proportion of two or more of glycerol, trimethylolpropane, pentaerythritol, xylitol or sorbitol.

[0045] In one embodiment, the catalyst I is one or a mixture of any proportion of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide or tetraethylammonium hydroxide.

[0046] In one embodiment, the bisphenol A epoxy resin is one of E55, E51, E44, E42, E35, and E20, or a mixture of any proportion of two or more thereof.

[0047] In one embodiment, the catalyst II is one or a mixture of any proportion of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole.

[0048] In one embodiment, the mass ratio of alicyclic epoxy group silane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is preferably 100: 68-132: 0.03-0.4: 506-1458: 0.03-0.4.

[0049] The above ratio is designed according to the functionality of different silane coupling agents and polyols. Exceeding this range will result in an excess of one component, causing the final product to contain unremovable impurities or produce gel.

[0050] In a preferred embodiment, the mass ratio of alicyclic epoxy group silane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is preferably 100:116:0.4:506:0.4.

[0051] In one embodiment, the photosensitive resin includes the organosilicon hyperbranched epoxy resin for photocurable 3D printing.

[0052] In one embodiment, the photosensitive resin is prepared from the following components in parts by weight:

[0053]

[0054] The method for preparing the photosensitive resin of this embodiment includes the following steps:

[0055] First, the photoinitiator TPO, diphenyliodonium hexafluorophosphate, 3-hydroxyoxetane and trimethylolpropane triacrylate are fully dissolved at 55-65°C to obtain a photosensitive diluent.

[0056] Then, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and the organosilicon hyperbranched epoxy resin for photocurable 3D printing are heated and stirred at 140-160° C.; then, after cooling to 75-85° C., the mixture is fully stirred with the photosensitive diluent to obtain the photosensitive resin.

[0057] The effects of the present invention are further illustrated by the following examples, but the embodiments of the present invention are not limited thereto.

[0058] Example 1

[0059] 246.37 g of 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 287.12 g of trimethylolpropane and 1 g of potassium hydroxide were added into a reactor, reacted at 40° C. for 48 h, by-products were removed by rotary evaporation, and then 1247.27 g of bisphenol A epoxy resin E55 and 1 g of 2-methylimidazole were added, reacted at 50° C. for 12 h to obtain a silicone hyperbranched epoxy resin.

[0060] In this embodiment, the mass ratio of the alicyclic epoxy group silane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is 100:116:0.4:506:0.4.

[0061] 10g of photoinitiator TPO and 60g of diphenyliodonium hexafluorophosphate, 300g of 3-hydroxyoxetane and 300g of trimethylolpropane triacrylate are fully dissolved at 60°C to obtain a photosensitive diluent, 300g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 100g of the above-mentioned organosilicon hyperbranched epoxy resin are heated and stirred at 150°C, cooled to 80°C and fully stirred with the above-mentioned photosensitive diluent to obtain a photosensitive resin containing organosilicon hyperbranched epoxy resin.

[0062] Example 2

[0063] 246.37 g of 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 285.91 g of pentaerythritol and 0.5 g of sodium hydroxide were added into a reactor, reacted at 60° C. for 36 h, by-products were removed by rotary evaporation, and then 1596 g of bisphenol A epoxy resin E51 and 0.5 g of 2-ethylimidazole were added, reacted at 70° C. for 10 h to obtain a silicone hyperbranched epoxy resin.

[0064] In this embodiment, the mass ratio of the alicyclic epoxy group silane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is 100:116:0.2:648:0.2.

[0065] 10g of photoinitiator TPO and 60g of diphenyliodonium hexafluorophosphate, 300g of 3-hydroxyoxetane and 300g of trimethylolpropane triacrylate are fully dissolved at 60°C to obtain a photosensitive diluent, 300g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 100g of the above-mentioned organosilicon hyperbranched epoxy resin are heated and stirred at 150°C, cooled to 80°C and fully stirred with the above-mentioned photosensitive diluent to obtain a photosensitive resin containing organosilicon hyperbranched epoxy resin.

[0066] Example 3

[0067] 288.45 g of 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, 197.08 g of propylene glycol and 0.4 g of tetramethylammonium hydroxide were added into a reactor, reacted at 80° C. for 12 h, by-products were removed by rotary evaporation, and then 1559.09 g of bisphenol A epoxy resin E44 and 0.4 g of 2-ethyl-4-methylimidazole were added, reacted at 90° C. for 8 h to obtain a silicone hyperbranched epoxy resin.

[0068] In this embodiment, the mass ratio of alicyclic epoxy group silane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is 100:68:0.13:541:0.13.

[0069] 10g of photoinitiator TPO and 60g of diphenyliodonium hexafluorophosphate, 300g of 3-hydroxyoxetane and 300g of trimethylolpropane triacrylate are fully dissolved at 60°C to obtain a photosensitive diluent, 300g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 100g of the above-mentioned organosilicon hyperbranched epoxy resin are heated and stirred at 150°C, cooled to 80°C and fully stirred with the above-mentioned photosensitive diluent to obtain a photosensitive resin containing organosilicon hyperbranched epoxy resin.

[0070] Example 4

[0071] 288.45 g of 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, 285.91 g of pentaerythritol and 0.25 g of potassium hydroxide were added into a reactor, reacted at 100° C. for 6 h, by-products were removed by rotary evaporation, and then 2000 g of bisphenol A epoxy resin E42 and 0.3 g of 2-phenylimidazole were added, and reacted at 110° C. for 6 h to obtain a silicone hyperbranched epoxy resin.

[0072] In this embodiment, the mass ratio of silicon of alicyclic epoxy group: alkane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is 100:116:0.09:694:0.1.

[0073] 10g of photoinitiator TPO and 60g of diphenyliodonium hexafluorophosphate, 300g of 3-hydroxyoxetane and 300g of trimethylolpropane triacrylate are fully dissolved at 60°C to obtain a photosensitive diluent, 300g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 100g of the above-mentioned organosilicon hyperbranched epoxy resin are heated and stirred at 150°C, cooled to 80°C and fully stirred with the above-mentioned photosensitive diluent to obtain a photosensitive resin containing organosilicon hyperbranched epoxy resin.

[0074] Example 5

[0075] 246.37 g of 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 325.59 g of xylitol and 0.15 g of potassium hydroxide were added into a reactor, reacted at 110° C. for 4 h, by-products were removed by rotary evaporation, and then 1960 g of bisphenol A epoxy resin E35 and 0.2 g of 2-methylimidazole were added, reacted at 130° C. for 4 h to obtain a silicone hyperbranched epoxy resin.

[0076] In this embodiment, the mass ratio of silicon of alicyclic epoxy group: alkane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is 100:132:0.06:797:0.08.

[0077] 10g of photoinitiator TPO and 60g of diphenyliodonium hexafluorophosphate, 300g of 3-hydroxyoxetane and 300g of trimethylolpropane triacrylate are fully dissolved at 60°C to obtain a photosensitive diluent, 300g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 100g of the above-mentioned organosilicon hyperbranched epoxy resin are heated and stirred at 150°C, cooled to 80°C and fully stirred with the above-mentioned photosensitive diluent to obtain a photosensitive resin containing organosilicon hyperbranched epoxy resin.

[0078] Example 6

[0079] 288.45 g of 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, 382.56 g of sorbitol and 0.1 g of sodium hydroxide were added into a reactor, reacted at 120° C. for 2 h, by-products were removed by rotary evaporation, and then 4200 g of bisphenol A epoxy resin E20 and 0.1 g of 2-ethylimidazole were added, reacted at 150° C. for 2 h to obtain a silicone hyperbranched epoxy resin.

[0080] In this embodiment, the mass ratio of silicon of alicyclic epoxy group: alkane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is 100:132:0.03:1458:0.03.

[0081] 10g of photoinitiator TPO and 60g of diphenyliodonium hexafluorophosphate, 300g of 3-hydroxyoxetane and 300g of trimethylolpropane triacrylate are fully dissolved at 60°C to obtain a photosensitive diluent, 300g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 100g of the above-mentioned organosilicon hyperbranched epoxy resin are heated and stirred at 150°C, cooled to 80°C and fully stirred with the above-mentioned photosensitive diluent to obtain a photosensitive resin containing organosilicon hyperbranched epoxy resin.

[0082] Comparative Example 1

[0083] 10 g of photoinitiator TPO and 60 g of diphenyliodonium hexafluorophosphate, 300 g of 3-hydroxyoxetane, 300 g of trimethylolpropane triacrylate and 400 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate were heated and stirred at 60° C. to obtain a photosensitive resin.

[0084] Comparative Example 2

[0085] 10g of photoinitiator TPO and 60g of diphenyliodonium hexafluorophosphate, 300g of 3-hydroxyoxetane and 300g of trimethylolpropane triacrylate were fully dissolved at 60°C to obtain a photosensitive diluent, 300g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 100g of HyPer E102 hyperbranched epoxy resin (Wuhan Hyperbranched Resin Technology Co., Ltd.) were heated and stirred at 150°C, cooled to 80°C and fully stirred with the above-mentioned photosensitive diluent to obtain a photosensitive resin containing silicone hyperbranched epoxy resin.

[0086] Comparative Example 3

[0087] 10g of photoinitiator TPO and 60g of diphenyliodonium hexafluorophosphate, 300g of 3-hydroxyoxetane and 300g of trimethylolpropane triacrylate were fully dissolved at 60°C to obtain a photosensitive diluent, 300g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 100g of CYE001 hyperbranched epoxy resin (Weihai Chenyuan Molecular New Materials Co., Ltd.) were heated and stirred at 150°C, cooled to 80°C and fully stirred with the above-mentioned photosensitive diluent to obtain a photosensitive resin containing silicone hyperbranched epoxy resin.

[0088] The photocurable resin obtained in the above examples and comparative examples was poured into an SLA photocurable printer for printing, and the obtained sample was washed and dried, and then placed in an ultraviolet curing box for curing for 20 minutes to obtain a 3D printed sample. The photosensitivity of each example and comparative example is shown in Table 1.

[0089] Table 1. Performance of photosensitive resins in various embodiments and comparative examples

[0090]

[0091]

[0092] As can be seen from Table 1, the photosensitive resin prepared by the organosilicon hyperbranched epoxy resin obtained in the embodiment of the present invention has a significantly higher elongation at break and impact strength than the photosensitive resin without adding hyperbranched epoxy resin in Comparative Example 1 and the photosensitive resin with adding commercially available hyperbranched epoxy resin in Comparative Examples 2 and 3, and its strength is not weakened, indicating that the organosilicon hyperbranched epoxy resin can effectively toughen the photocurable resin, greatly improving the toughness of the conventional photocurable 3D printed parts.

[0093] The present invention is not limited to the above embodiments, and all improvements and substitutions made according to the principles of the present invention are within the protection scope of the present invention.

Claims

1. A method for preparing a silicone hyperbranched epoxy resin for photocuring 3D printing, characterized in that: The steps include: Add a silane coupling agent with alicyclic epoxy groups, polyether polyol and catalyst I into a reactor, react at 40-120° C. for 2-48 hours, and remove by-products by rotary evaporation; Then, bisphenol A epoxy resin and catalyst II are added, and the mixture is reacted at 50-150° C. for 2-12 hours to obtain the organosilicon hyperbranched epoxy resin for photocuring 3D printing; The catalyst I is a basic catalyst, and the catalyst II is an imidazole catalyst.

2. The method for preparing a silicone hyperbranched epoxy resin for photocuring 3D printing according to claim 1, characterized in that: The silane coupling agent with alicyclic epoxy groups is one of 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane or a mixture of the two in any proportion; The polyether polyol is one of glycerol, trimethylolpropane, pentaerythritol, xylitol or sorbitol, or a mixture of two or more of them in any proportion.

3. The method for preparing a silicone hyperbranched epoxy resin for photocuring 3D printing according to claim 1, characterized in that: The catalyst I is one of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide or tetraethylammonium hydroxide, or a mixture of two or more of them in any proportion.

4. The method for preparing a silicone hyperbranched epoxy resin for photocuring 3D printing according to claim 1, characterized in that: The bisphenol A epoxy resin is one of E55, E51, E44, E42, E35 or E20, or a mixture of two or more of them in any proportion.

5. The method for preparing a silicone hyperbranched epoxy resin for photocuring 3D printing according to claim 1, characterized in that: The catalyst II is one of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole, or a mixture of two or more of them in any proportion.

6. The method for preparing a silicone hyperbranched epoxy resin for photocuring 3D printing according to claim 1, characterized in that: The mass ratio of alicyclic epoxy group silane coupling agent: polyol: catalyst I: bisphenol A epoxy resin: catalyst II is 100: 68-132: 0.03-0.4: 506-1458: 0.03-0.

4.

7. An organosilicon hyperbranched epoxy resin for photocuring 3D printing, characterized in that: Prepared by the method according to any one of claims 1 to 6.

8. The use of a silicone hyperbranched epoxy resin for photocuring 3D printing according to claim 7, characterized in that: The organosilicon hyperbranched epoxy resin for photocuring 3D printing is used to prepare photosensitive resin.

9. A photosensitive resin, characterized in that: Including the organosilicon hyperbranched epoxy resin for photocuring 3D printing as described in claim 7.

10. The photosensitive resin according to claim 9, characterized in that: The photosensitive resin further comprises 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, a photoinitiator TPO, diphenyliodonium hexafluorophosphate, 3-hydroxyoxetane, and trimethylolpropane triacrylate, and each component is prepared in the following mass fraction ratio:

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