A transparent light-curing modified resin with low thermal expansion coefficient and preparation method thereof

Abstract

The invention discloses a transparent light-curing modified resin with a low thermal expansion coefficient and a preparation method thereof. The molar ratio of each raw material of the resin is: polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol trifunctional epoxy resin = 2:1.25:0.09:0.55. The method comprises: step S1, nitrogen protection, adding polydimethyl diketone silane and dicyclopentadiene phenolic resin into a reactor, stirring at room temperature for 20 minutes to mix evenly; step S2, adding hypochlorous acid to adjust the pH value to 4-5, maintaining nitrogen protection; step S3, adding dibutyltin dilaurate into the reactor, and reflux reaction under heating and stirring; step S4, adding aminophenol trifunctional epoxy resin into the reactor, and reflux reaction under heating; step S5, reducing pressure distillation after the reaction, and the remaining substance is the transparent light-curing modified resin with a low thermal expansion coefficient. It has a higher glass transition temperature, lower water absorption, and a lower thermal expansion coefficient in different temperature ranges.

Description

Technical Field

[0001] The present invention relates to the field of organic synthetic resins, and in particular to a transparent light-curing modified resin with a low thermal expansion coefficient and a preparation method thereof. Background Art

[0002] With the rapid development of science and technology, various types of precision manufacturing equipment have emerged in an endless stream. During device assembly, adhesives are often required due to the unique nature of substrates or connection methods. With the increasing sophistication of electronic products, the requirements for adhesives are increasing. In particular, some components or optical devices are extremely precise, requiring strict control over the deformation of the adhesive at different temperatures. Therefore, the adhesive must have a low thermal expansion coefficient. Currently, this is achieved primarily by adding large amounts of fillers. This significantly increases the viscosity of the adhesive, impacting operation. Furthermore, in some optical device assembly processes, the addition of large amounts of fillers can cause the adhesive to lose transparency, making it unusable.

[0003] In view of this, the present invention is proposed. Summary of the Invention

[0004] In response to the above-mentioned deficiencies in the prior art, the present invention provides a transparent photocurable modified resin with a low thermal expansion coefficient and a preparation method, which can achieve a lower thermal expansion coefficient without adding fillers, thereby not affecting the transparency of the product, so that it can be used in working conditions such as optical equipment assembly.

[0005] The purpose of the present invention is that the technical solution adopted by the present invention is as follows:

[0006] A transparent light-curing modified resin with a low thermal expansion coefficient is prepared from the following raw materials in a molar ratio of: polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol-based trifunctional epoxy resin = 2:1.25:0.09:0.55.

[0007] A method for preparing a transparent light-curable modified resin with a low thermal expansion coefficient according to the present invention comprises the following steps:

[0008] Take the raw materials according to the formula ratio of the present invention;

[0009] Step S1, under nitrogen protection, adding polydimethyl diketone silane and dicyclopentadiene phenolic resin into a reaction kettle, and stirring at room temperature for 20 minutes until the mixture is uniformly mixed;

[0010] Step S2, adding hypochlorous acid to adjust the pH value to 4-5, maintaining nitrogen protection during the process;

[0011] Step S3, adding dibutyltin dilaurate to the reaction kettle, and performing a reflux reaction under a heating and stirring environment;

[0012] Step S4, adding an aminophenol-based trifunctional epoxy resin into a reaction vessel, and performing a reflux reaction under heating conditions;

[0013] Step S5: After the reaction is completed, vacuum distillation is performed, and the remaining substance is the prepared transparent light-curable modified resin with a low thermal expansion coefficient.

[0014] Compared with the prior art, the main advantages of the low thermal expansion coefficient transparent light-curable modified resin of the present invention are as follows:

[0015] (1) Low thermal expansion coefficient can be achieved without adding a large amount of filler;

[0016] (2) Products cured with the resin of the present invention have a higher glass transition temperature and more ideal thermal stability;

[0017] (3) The product cured with the resin of the present invention has low water absorption;

[0018] The above properties make the resin of the present invention suitable for use in the assembly of precision electronic equipment, especially precision optical equipment. DETAILED DESCRIPTION

[0019] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them, and do not constitute a limitation of the present invention. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0020] First, the following terms may be used in this article:

[0021] The terms "include," "comprises," "contains," "has," or other similar expressions should be interpreted as non-exclusive. For example, "including certain technical features (such as raw materials, components, ingredients, carriers, dosage forms, materials, dimensions, parts, components, mechanisms, devices, steps, procedures, methods, reaction conditions, processing conditions, parameters, algorithms, signals, data, products, or manufactured articles)" should be interpreted as including not only the technical features explicitly listed, but also other technical features known in the art that are not explicitly listed.

[0022] The term "parts by weight" refers to the mass ratio of multiple components. For example, if component X is x parts by weight and component Y is y parts by weight, the mass ratio of component X to component Y is x:y. One part by weight can represent any mass, for example, 1 part by weight can represent 1 kg or 3.1415926 kg. The sum of the parts by weight of all components is not necessarily 100 parts and can be greater than, less than, or equal to 100 parts. Unless otherwise specified, parts, ratios, and percentages herein are by mass.

[0023] When concentration, temperature, pressure, size or other parameters are expressed in the form of a numerical range, the numerical range should be understood to specifically disclose all ranges formed by the pairing of any upper limit, lower limit, or preferred value within the numerical range, regardless of whether the range is explicitly stated. For example, if a numerical range of "2 to 8" is stated, the numerical range should be interpreted as including ranges of "2 to 7," "2 to 6," "5 to 7," "3 to 4 and 6 to 7," "3 to 5 and 7," "2 and 5 to 7," etc. Unless otherwise specified, the numerical ranges stated herein include both their endpoints and all integers and fractions within the numerical range.

[0024] The transparent light-curable modified resin with a low thermal expansion coefficient and its preparation method provided by the present invention are described in detail below. Any details not described in the examples of the present invention are prior art known to those skilled in the art. In the examples of the present invention, where specific conditions are not specified, the reaction was carried out according to conventional conditions in the art or the conditions recommended by the manufacturer. Reagents or instruments used in the present invention, where the manufacturer is not specified, are all commercially available conventional products.

[0025] The following describes in detail a transparent light-curable modified resin with a low thermal expansion coefficient and a preparation method thereof provided by the present invention. The contents not described in detail in the embodiments of the present invention belong to the prior art known to professionals in this field.

[0026] An embodiment of the present invention provides a transparent light-curable modified resin with a low thermal expansion coefficient. The modified resin is made of the following raw materials in a molar ratio of: polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol trifunctional epoxy resin = 2:1.25:0.09:0.55.

[0027] The present invention also provides a method for preparing the transparent light-curable modified resin with a low thermal expansion coefficient, comprising the following steps:

[0028] Step S1: under nitrogen protection, polydimethyl diketone silane and dicyclopentadiene phenolic resin are added to a reaction kettle and stirred at room temperature for 20 minutes until the mixture is uniformly mixed;

[0029] Step S2, adding hypochlorous acid to adjust the pH value to 4-5, maintaining nitrogen protection during the process;

[0030] Step S3, adding dibutyltin dilaurate to the reaction kettle, and performing a reflux reaction under a heating and stirring environment;

[0031] Step S4, adding an aminophenol-based trifunctional epoxy resin into a reaction vessel, and performing a reflux reaction under heating conditions;

[0032] Step S5: After the reaction is completed, vacuum distillation is performed, and the remaining substance is the transparent light-curable modified resin with a low thermal expansion coefficient.

[0033] Furthermore, the molar ratio of the raw materials used in the present invention is polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol trifunctional epoxy resin = 2:1.25:0.09:0.55.

[0034] Furthermore, the degree of polymerization of the polydimethyldiketone silane in the above step 1 is in the range of 3 to 7.

[0035] Furthermore, in the above step 1, the degree of polymerization of the dicyclopentadiene phenolic resin is 2 to 3.

[0036] Furthermore, the stirring speed in the above step 1 is 150-200 rpm.

[0037] Furthermore, the heating temperature in the above step 3 is 105-200°C.

[0038] Furthermore, the stirring speed in the above step 3 is 150-350 rpm; preferably, the stirring speed in step 3 is 150-250 rpm.

[0039] Furthermore, the stirring time in the above step 3 is 3 to 5 hours; preferably, the stirring time in step 3 is 2 to 3 hours.

[0040] Furthermore, the heating temperature in the above step 4 is 105-200°C.

[0041] Furthermore, in the above step 3, the stirring speed is 150-250 rpm.

[0042] In order to more clearly demonstrate the technical solution and technical effects provided by the present invention, the transparent photocurable modified resin with low thermal expansion coefficient and the preparation method provided by the embodiments of the present invention are described in detail below with reference to specific embodiments. Example

[0043] This embodiment provides a transparent light-curable modified resin with a low thermal expansion coefficient. The raw materials of the resin are polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol trifunctional epoxy resin in a ratio of 2:1.25:0.09:0.55. The preparation method of the transparent light-curable modified resin with a low thermal expansion coefficient is as follows:

[0044] Step S1, under nitrogen protection, polydimethyldiketone silane with a degree of polymerization of 4 and dicyclopentadiene phenolic resin with a degree of polymerization of 2 are added into a reaction kettle, and stirred at room temperature for 20 minutes until they are uniformly mixed;

[0045] Step S2, adding hypochlorous acid to adjust the pH value to 4-5, maintaining nitrogen protection during the process; it can be seen that in this step, only a small amount of hypochlorous acid is needed to adjust the pH value of the system to 4-5;

[0046] Step S3, adding dibutyltin dilaurate to the reaction kettle, stirring at 145° C. and 150 rpm, and performing reflux reaction for 4 hours;

[0047] Step S4, adding aminophenol-based trifunctional epoxy resin into the reaction kettle, stirring at 145° C. and 150 rpm, and performing reflux reaction for 2 hours;

[0048] Step S5: After the reaction is completed, vacuum distillation is performed, and the remaining substance is the transparent light-curable modified resin with a low thermal expansion coefficient. Example

[0049] This embodiment provides a transparent light-curable modified resin with a low thermal expansion coefficient. The raw materials of the resin are polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol trifunctional epoxy resin in a ratio of 2:1.25:0.09:0.55. The preparation method of the transparent light-curable modified resin with a low thermal expansion coefficient is as follows:

[0050] Step S1, under nitrogen protection, polydimethyldiketone silane with a degree of polymerization of 3 and dicyclopentadiene phenolic resin with a degree of polymerization of 3 are added to a reaction kettle, and stirred at room temperature for 20 minutes until they are uniformly mixed;

[0051] Step S2, adding hypochlorous acid to adjust the pH value to 4-5, maintaining nitrogen protection during the process; it can be seen that in this step, only a small amount of hypochlorous acid is needed to adjust the pH value of the system to 4-5;

[0052] Step S3, adding dibutyltin dilaurate to the reaction kettle, stirring at 155° C. and 180 rpm, and performing reflux reaction for 5 hours;

[0053] Step S4, adding an aminophenol-based trifunctional epoxy resin into the reaction kettle, stirring at 175° C. and 230 rpm, and performing a reflux reaction for 3 hours;

[0054] Step S5: After the reaction is completed, vacuum distillation is performed, and the remaining substance is the transparent light-curable modified resin with a low thermal expansion coefficient. Example

[0055] This embodiment provides a transparent light-curable modified resin with a low thermal expansion coefficient. The raw materials of the resin are polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol trifunctional epoxy resin in a ratio of 2:1.25:0.09:0.55. The preparation method of the transparent light-curable modified resin with a low thermal expansion coefficient is as follows:

[0056] Step S1, under nitrogen protection, polydimethyldiketone silane with a degree of polymerization of 4 and dicyclopentadiene phenolic resin with a degree of polymerization of 3 are added to a reaction kettle, and stirred at room temperature for 20 minutes until they are uniformly mixed;

[0057] Step S2, adding hypochlorous acid to adjust the pH value to 4-5, maintaining nitrogen protection during the process; it can be seen that in this step, only a small amount of hypochlorous acid is needed to adjust the pH value of the system to 4-5;

[0058] Step S3, adding dibutyltin dilaurate to the reaction kettle, stirring at 125° C. and 150 rpm, and performing reflux reaction for 5 hours;

[0059] Step S4, adding aminophenol-based trifunctional epoxy resin into the reaction kettle, stirring at 170° C. and 150 rpm, and performing reflux reaction for 2 hours;

[0060] Step S5: After the reaction is completed, vacuum distillation is performed, and the remaining substance is the transparent light-curable modified resin with a low thermal expansion coefficient. Example

[0061] This embodiment provides a transparent light-curable modified resin with a low thermal expansion coefficient. The raw materials of the resin are polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol trifunctional epoxy resin in a ratio of 2:1.25:0.09:0.55. The preparation method of the transparent light-curable modified resin with a low thermal expansion coefficient is as follows:

[0062] Step S1, under nitrogen protection, polydimethyldiketone silane with a degree of polymerization of 7 and dicyclopentadiene phenolic resin with a degree of polymerization of 3 are added to a reaction kettle, and stirred at room temperature for 20 minutes until they are uniformly mixed;

[0063] Step S2, adding hypochlorous acid to adjust the pH value to 4-5, maintaining nitrogen protection during the process; it can be seen that in this step, only a small amount of hypochlorous acid is needed to adjust the pH value of the system to 4-5;

[0064] Step S3, adding dibutyltin dilaurate to the reaction kettle, stirring at 185° C. and 200 rpm, and performing reflux reaction for 3 hours;

[0065] Step S4, adding aminophenol-based trifunctional epoxy resin into the reaction kettle, stirring at 185° C. and 240 rpm, and performing reflux reaction for 2 hours;

[0066] Step S5: After the reaction is completed, vacuum distillation is performed, and the remaining substance is the transparent light-curable modified resin with a low thermal expansion coefficient.

[0067] Resin performance test sample preparation:

[0068] Prepare samples according to the following scheme and compare the performance differences of several different resins.

[0069] The specific schemes using different resins are as follows:

[0070] After the sample is prepared according to the above method, it is fully irradiated with a 365nm light source and then tested.

[0071] Performance testing:

[0072] The present invention adopts the following detection method:

[0073] (1) Glass transition temperature: tested by TMA puncture method.

[0074] (2) Thermal expansion coefficient: Tested using TMA according to GB / T 36800.2 to test the thermal expansion coefficient before the glass transition temperature (α1) and the thermal expansion coefficient after the glass transition temperature (α2).

[0075] (3) Water absorption rate: Prepare a rubber block of about 10 g and soak it in 100°C water for 4 h, then test the weight gain rate.

[0076] (3) Transparency: visual observation.

[0077] Test the above samples according to the test requirements and record the results in the following table:

[0078] Plan No. Glass transition temperature / ℃ Thermal expansion coefficient (α1) / ppm / K Thermal expansion coefficient (α2) / ppm / K Water absorption / % transparency 1 109 21 55 0.2 transparent 2 104 23 49 0.4 transparent 3 105 22 52 0.2 transparent 4 112 25 45 0.3 transparent 5 39 42 113 2.4 transparent 6 46 39 105 2.2 transparent 7 52 36 92 2.9 transparent 8 52 41 94 1.8 transparent

[0079] As can be seen from the above table, compared with the adhesives in the prior art, the samples prepared using Examples 1 to 4 of the present invention have a higher glass transition temperature and lower water absorption rate without adding fillers to maintain transparency. At the same time, they have a lower thermal expansion coefficient in different temperature ranges. In particular, when the temperature reaches above the glass transition temperature of the sample, the reduction in the thermal expansion coefficient is more obvious compared with other resins.

[0080] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims. The information disclosed in the background technology section of this article is only intended to deepen the understanding of the overall background technology of the present invention, and should not be regarded as an admission or any form of implication that the information constitutes prior art already known to those skilled in the art.

Claims

1. A transparent light-curable modified resin with a low thermal expansion coefficient, characterized in that: The resin is prepared from the following raw materials in a molar ratio of: polydimethyl diketone silane: dicyclopentadiene phenolic resin: dibutyltin dilaurate: aminophenol trifunctional epoxy resin = 2:1.25:0.09:0.55; The degree of polymerization of the polydimethyl diketone silane is in the range of 3 to 7; The degree of polymerization of the dicyclopentadiene phenolic resin is 2 to 3; The preparation method of the resin comprises the following steps: Take each raw material according to the above formula ratio; Step S1, under nitrogen protection, adding polydimethyl diketone silane and dicyclopentadiene phenolic resin into a reaction kettle, and stirring at room temperature for 20 minutes until the mixture is uniformly mixed; Step S2, adding hypochlorous acid to adjust the pH value to 4-5, while maintaining nitrogen protection; Step S3, adding dibutyltin dilaurate into the reaction kettle, and performing reflux reaction under heating and stirring; Step S4, adding aminophenol-based trifunctional epoxy resin into a reaction kettle, and performing a reflux reaction under heating conditions; Step S5, after the reaction is completed, vacuum distillation is performed, and the remaining substance is the obtained transparent light-curable modified resin with low thermal expansion coefficient.

2. A method for preparing the transparent photocurable modified resin with low thermal expansion coefficient according to claim 1, characterized in that: The following steps are involved: Take the raw materials according to the formula ratio of claim 1; Step S1, under nitrogen protection, adding polydimethyl diketone silane and dicyclopentadiene phenolic resin into a reaction kettle, and stirring at room temperature for 20 minutes until the mixture is uniformly mixed; the polymerization degree of the polydimethyl diketone silane is in the range of 3 to 7, and the polymerization degree of the dicyclopentadiene phenolic resin is in the range of 2 to 3; Step S2, adding hypochlorous acid to adjust the pH value to 4-5, while maintaining nitrogen protection; Step S3, adding dibutyltin dilaurate into the reaction kettle, and performing reflux reaction under heating and stirring; Step S4, adding aminophenol-based trifunctional epoxy resin into a reaction kettle, and performing a reflux reaction under heating conditions; Step S5, after the reaction is completed, vacuum distillation is performed, and the remaining substance is the obtained transparent light-curable modified resin with low thermal expansion coefficient.

3. The method for preparing a transparent light-curable modified resin with a low thermal expansion coefficient according to claim 2, characterized in that: The stirring speed in step S1 is 150-200 rpm.

4. The method for preparing a transparent light-curable modified resin with a low thermal expansion coefficient according to claim 2, characterized in that: The heating temperature in step S3 is 105-200° C.; In step S3, the stirring speed is 150-350 rpm, and the stirring time is 3-5 hours.

5. The method for preparing a transparent light-curable modified resin with a low thermal expansion coefficient according to claim 2, characterized in that: The heating temperature in step S4 is 105-200°C.