CN113201104A - Cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant and preparation method thereof - Google Patents

Cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant and preparation method thereof Download PDF

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CN113201104A
CN113201104A CN202110692506.3A CN202110692506A CN113201104A CN 113201104 A CN113201104 A CN 113201104A CN 202110692506 A CN202110692506 A CN 202110692506A CN 113201104 A CN113201104 A CN 113201104A
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epoxy resin
cage
dielectric constant
polysilsesquioxane
low dielectric
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CN113201104B (en
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陈玉伟
胡振东
王泉
槐凯
崔欣
魏怀笑
吴韦菲
张白浪
胡金金
车俊伯
张田砚
张建明
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Shang Hai Yinai New Material Technology Ltd
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Qingdao University of Science and Technology
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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    • C08F290/064Polymers containing more than one epoxy group per molecule

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Abstract

The invention relates to the technical field of integrated circuits, in particular to a cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant and a preparation method thereof. The cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant is prepared from modified epoxy resin, cage type polysilsesquioxane and a photoinitiator; the modified epoxy resin is used after ring-opening modification, double bonds are introduced into an epoxy resin chain, the double bonds have high activity, can be subjected to free polymerization, have high curing speed and low curing temperature, and can be cured and molded at room temperature in a photocuring mode, so that the cage-type polysilsesquioxane/epoxy resin nanocomposite prepared by the invention is more suitable for serving as a bonding and packaging material for chips and circuit boards.

Description

Cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant and preparation method thereof
Technical Field
The invention relates to the technical field of integrated circuits, in particular to a packaging material and an insulating material for electronic devices, and more particularly relates to a cage type polysilsesquioxane/epoxy resin nano composite material with a low dielectric constant and a preparation method thereof.
Technical Field
The 5G communication technology enables the production and life of people to be more efficient and faster, in recent years, people can deeply feel the influence of electronic products on the life of people, and the life quality of people is greatly improved. The electronic packaging material is used as an important component of the electronic component, and can effectively protect the electronic component from being interfered by the external environment, and ensure effective transmission and stable function of signals. The advent of new generation electronic products has put higher demands on the performance of electronic packaging materials, and under such a trend, conventional packaging materials have gradually failed to meet the stringent requirements of very large scale integrated circuits, and thus it is necessary to prepare dielectric materials having excellent electrical properties by effective means.
Electronic packaging materials are required to have a low dielectric constant and high insulation properties. At present, the epoxy resin has the characteristics of excellent cohesiveness and insulativity and is widely used in the electrical and electronic industry; however, the dielectric constant of the epoxy resin material used in the electrical and electronic industry is about 4, and the low dielectric constant material used in 5G communication electronic equipment cannot be met, so it is very important to develop a low dielectric constant material that can be used in 5G communication electronic equipment.
Disclosure of Invention
In order to solve the above-mentioned conventional problems, an object of the present invention is to provide a cage type Polysilsesquioxane (POSS)/epoxy nanocomposite with a low dielectric constant and a method for preparing the same.
The invention can be realized by the following technical scheme:
a cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant is prepared from the following raw materials: modified epoxy resin, cage type polysilsesquioxane and photoinitiator;
the addition amount of the cage type polysilsesquioxane accounts for 10-50 percent of the total amount of the cage type polysilsesquioxane and the modified epoxy resin, and is preferably 40 percent;
the addition amount of the photoinitiator accounts for 0.5-2% of the total amount of the cage type polysilsesquioxane and the modified epoxy resin, and is preferably 1%;
the modified epoxy resin is prepared from the following raw materials: epoxy resins, diluents, ring-opening agents and catalysts;
the mass ratio of the epoxy resin, the diluent, the ring-opening agent and the catalyst is (80-120): (10-50): (20-60): (0.1-1), preferably 103: 28: 48: 0.44;
further, the cage-type polysilsesquioxane is methacryloxypropyl cage-type polysilsesquioxane;
further, the epoxy resin is bisphenol a epoxy resin (more preferably E51);
further, the ring-opening agent is selected from one of primary amine, secondary amine, phenolic compound and carboxylic acid compound, and is more preferably methacrylic acid;
further, the catalyst is triphenylphosphine;
further, the diluent is hydroxyethyl methacrylate;
further, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
The invention also provides a preparation method of the cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant, which comprises the following steps:
(1) modification of epoxy resin: adding epoxy resin, a ring-opening agent and a catalyst into a reaction container, and carrying out a ring-opening reaction to obtain methacrylic acid based epoxy resin; then adding a diluent to adjust the viscosity to obtain a methacrylic acid based epoxy resin mixture, namely modified epoxy resin;
(2) uniformly mixing the modified epoxy resin obtained in the step (1) and the cage-type polysilsesquioxane, and then adding a photoinitiator into the mixture to perform curing molding through ultraviolet light (preferably, after uniform mixing, firstly eliminating bubbles in a system, and then adding the photoinitiator to perform curing molding).
Further, the ring-opening reaction in the step (1) is carried out at 100-150 ℃, the reaction time is 4-12h (preferably at 120-125 ℃ for 6h), when the acid value of the system is less than 10KOH/(mg/g), the temperature is reduced to below 90 ℃, and then the diluent is added into the system.
Further, the catalyst in the step (1) is added for multiple times, and the temperature of the system is increased by 3-4 ℃ while each time of adding.
Furthermore, the preparation method of the cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant specifically comprises the following steps:
(a) adding bisphenol A epoxy resin into a three-neck flask, heating to 80 ℃, uniformly stirring, adding methacrylic acid, heating to 110 ℃, adding a triphenylphosphine catalyst for four times, heating to 3-4 ℃ after each addition, reacting at the final reaction temperature of 120-125 ℃ for 6 hours at 120-125 ℃, cooling to 80 ℃ when the acid value of the system is less than 10KOH/(mg/g), adding 28g of hydroxyethyl methacrylate, and uniformly stirring to obtain a methacrylic acid-based epoxy resin mixture, namely the modified epoxy resin;
(b) and preparing a sample:
uniformly stirring and mixing the modified epoxy resin and the methacryloxypropyl cage-type polysilsesquioxane, adding a photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide into the mixture, uniformly stirring the mixture, then placing the mixture into an oven at 70 ℃ to eliminate bubbles, pouring the mixture into a mold, and irradiating the mold for 2-3 min by using an ultraviolet lamp to cure and mold the resin to obtain the cage-type polysilsesquioxane/epoxy resin nano composite material with a low dielectric constant.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) polyhedral oligomeric silsesquioxanes (polysilsesquioxanes) are hollow nanoparticles with a nano structure and a high specific surface area, POSS belongs to a nano-scale silicon dioxide/siloxane hybrid, molecules are in a cage structure, the molecular size is usually 1-3nm, an inorganic framework core is formed by Si-O, and the periphery of the inorganic framework core is surrounded by organic groups. The compound has excellent reactivity, heat resistance, flame retardance, porosity and nano-size effect. The nano particles with hollow structures are introduced into the polymer, and the good dispersion of the nano particles in the composite material is ensured, so that a nano-pore structure can be formed, and the dielectric constant of the material can be effectively reduced.
(2) The molecular chain terminal of the epoxy resin contains double bonds through modification, the molecular chains of the modified epoxy resin and the nano particle POSS both contain double bonds, the double bonds have higher activity, can be subjected to free polymerization, have high curing speed and low curing temperature, and can be cured and molded at room temperature in a photocuring mode, so that the epoxy resin nano composite material prepared by the method is more suitable for being used as a bonding and packaging material of chips and circuit boards.
Drawings
FIG. 1 is a Fourier transform infrared spectrum before and after modification of the epoxy resin in the example.
FIG. 2 is a graph of the dielectric constant of the low dielectric constant epoxy nanocomposite prepared in the examples.
FIG. 3 is a reaction mechanism diagram of the preparation of the epoxy resin nanocomposite with low dielectric constant according to the technical scheme of the present invention.
Detailed Description
The technical solution of the present invention is described in detail below with reference to examples.
The embodiment provides an epoxy resin nano composite material with low dielectric constant, which is prepared by the following method:
(1) preparing raw materials:
bisphenol a epoxy resin E51103g, specifically south asian epoxy 128 resin;
50g of nano particles; the nano-particles are methacryloxypropyl polyhedral oligomeric silsesquioxane (POSS);
48g of ring-opening agent, wherein the ring-opening agent is methacrylic acid;
0.44g of catalyst, namely triphenylphosphine;
28g of diluent, wherein the diluent is hydroxyethyl methacrylate;
and the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.
(2) Modification of epoxy resins
Adding 103g of bisphenol A epoxy resin into a three-neck flask, heating to 80 ℃, stirring at a rotating speed of 150r/min for 6min, adding 48g of methacrylic acid, heating to 110 ℃, adding a triphenylphosphine catalyst into the mixture in four times, adding 0.1g, 0.12g and 0.12g of the triphenylphosphine catalyst into the mixture each time, increasing the temperature by 3-4 ℃ after each addition, finally reacting at 120-125 ℃, reacting at 120-125 ℃ for 6h after the addition is finished, cooling to 80 ℃ when the acid value of the system is less than 10KOH/(mg/g), adding 28g of hydroxyethyl methacrylate into the mixture, and stirring uniformly to obtain the modified epoxy resin, wherein the schematic reaction formula is shown in the following formula.
Figure BDA0003126679450000041
(3) And preparing a sample:
the preparation method comprises the steps of stirring and mixing nano particle POSS and modified epoxy resin uniformly to obtain nano POSS/epoxy resin, adding photoinitiator (2,4, 6-trimethylbenzoyl chloride) diphenyl phosphine oxide accounting for 1% of the total amount of the nano particle POSS and the modified epoxy resin, stirring uniformly, and then putting the mixture into an oven at 70 ℃ for 5min to eliminate bubbles. And then pouring the resin into a mold, and irradiating the resin for 2-3 min by using an ultraviolet lamp to cure and mold the resin to obtain the final epoxy resin nano composite material with low dielectric constant.
During the operation of the step (3), POSS nanoparticles with different contents are respectively selected to investigate the influence of the POSS nanoparticles on the dielectric constant, wherein the mass fractions of the POSS nanoparticles to the total mass of the POSS nanoparticles and the modified resin are respectively 0 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt%, that is, the mass ratios of the POSS nanoparticles to the modified epoxy resin are respectively 0: 10; 1: 9; 2: 8; 3: 7; 4: 6; 5: 5.
fourier transform infrared spectrograms of the epoxy resin and the modified epoxy resin in this example are shown in FIG. 1, and it can be seen that the modified epoxy resin is about 3400cm in comparison with the epoxy resin before modification-1the-OH stretching vibration peak of the hydroxyl group is enhanced at 830cm-1The characteristic absorption peak of the left and right epoxy groups C-O-C is weakened and appears at 1740cm-1The stretching vibration peak of ester carbonyl C ═ O appears at the left and right, and is 1620cm-1Stretching vibration peaks of carbon-carbon double bonds C ═ C appear on the left and right. The modification of the epoxy resin was successful in this example.
The dielectric constants of the prepared samples are shown in FIG. 2 (wherein EP represents the substance obtained by not adding POSS particles in the step (3), POSS/EP-10% represents the POSS nanoparticles accounting for 10% of the total mass of the POSS nanoparticles and the modified resin, and the others are as described above), it can be seen that, after the polyhedral oligomeric silsesquioxane (POSS) nanoparticles are added, the nanocomposite with low dielectric constant is prepared, and the dielectric constants of the POSS/EP nanocomposites with POSS contents of 0%, 10%, 20%, 30%, 40% and 50% are 4.0, 3.0, 2.8, 2.7, 2.2 and 2.6 respectively at a temperature of 25 ℃ and a frequency of 1 MHz. Wherein the nano composite material with POSS content of 40% (POSS/EP-40%) has the lowest dielectric constant of 2.2. The data show that the cage type Polysilsesquioxane (POSS)/epoxy resin nano composite material with low dielectric constant is prepared by the method. The above dielectric constants were measured by using an Alpha-A type wide-band dielectric impedance spectrometer (Novocontrl, Germany).
FIG. 3 is a schematic diagram of the low dielectric constant mechanism of cage Polysilsesquioxane (POSS)/epoxy resin nanocomposite, which utilizes the nano structure and high specific surface area of cage polysilsesquioxane, and the molecule of the cage polysilsesquioxane is in a cage structure, and Si-O forms an inorganic framework core, and the periphery of the cage polysilsesquioxane is surrounded by organic groups. Has excellent reactivity, heat resistance, flame retardance, porosity and nano-size effect. The nano particles with hollow structures are introduced into the polymer, the good dispersion of the nano particles in the composite material is ensured, the nano pore structure can be formed, the dielectric constant of the material can be effectively reduced, and the aim of preparing the epoxy resin nano composite material with low dielectric constant is finally achieved.

Claims (7)

1. A cage type polysilsesquioxane/epoxy resin nano composite material with low dielectric constant is prepared from the following raw materials: modified epoxy resin, cage type polysilsesquioxane and photoinitiator;
the addition amount of the cage type polysilsesquioxane accounts for 10-50 percent of the total amount of the cage type polysilsesquioxane and the modified epoxy resin, and is preferably 40 percent;
the addition amount of the photoinitiator accounts for 0.5-2% of the total amount of the cage type polysilsesquioxane and the modified epoxy resin, and is preferably 1%;
the modified epoxy resin is prepared from the following raw materials: epoxy resins, diluents, ring-opening agents and catalysts;
the mass ratio of the epoxy resin, the diluent, the ring-opening agent and the catalyst is (80-120): (10-50): (20-60): (0.1-1).
2. The low dielectric constant cage polysilsesquioxane/epoxy nanocomposite of claim 1 wherein the cage polysilsesquioxane is a methacryloxypropyl cage polysilsesquioxane.
3. The low dielectric constant cage-type polysilsesquioxane/epoxy nanocomposite of claim 2 wherein the epoxy resin is a bisphenol a epoxy resin;
the ring-opening agent is selected from one of primary amine, secondary amine, phenolic compounds and carboxylic acid compounds;
the catalyst is triphenylphosphine;
the diluent is hydroxyethyl methacrylate.
4. The low dielectric constant cage polysilsesquioxane/epoxy nanocomposite of claim 3, wherein the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
5. A method for preparing the low dielectric constant cage-type polysilsesquioxane/epoxy nanocomposite of any of claims 1-4, comprising the steps of:
(1) modification of epoxy resin: adding epoxy resin, a ring-opening agent and a catalyst into a reaction container, and carrying out a ring-opening reaction to obtain methacrylic acid based epoxy resin; then adding a diluent to adjust the viscosity to obtain a methacrylic acid based epoxy resin mixture, namely modified epoxy resin;
(2) and (2) uniformly mixing the modified epoxy resin obtained in the step (1) with the cage-type polysilsesquioxane, adding a photoinitiator into the mixture, and curing and molding the mixture through ultraviolet light.
6. The preparation method according to claim 5, wherein the ring-opening reaction in the step (1) is carried out at 100-150 ℃, the reaction time is 4-12h, when the acid value of the system is less than 10KOH/(mg/g), the temperature is reduced to below 90 ℃, and then the diluent is added into the system.
7. The preparation method according to claim 5, wherein the catalyst is added in multiple times in step (1), and the temperature of the system is increased by 3-4 ℃ while each time of addition.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114539876A (en) * 2022-03-01 2022-05-27 高尧 Corrosion-resistant heat-dissipation protective coating and preparation method thereof
CN114806091A (en) * 2022-05-18 2022-07-29 陈全辉 POSS-CuPc-SiO 2 Preparation method of modified epoxy resin composite material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304960A (en) * 2013-05-23 2013-09-18 厦门大学 Preparation method of co-continuous POSS (Polyhedral Oligomeric Silsesquioxane)-epoxy modified resin
CN104845049A (en) * 2015-06-05 2015-08-19 厦门大学 Preparation method of phosphorus-containing flame-retardant organic-inorganic hybrid silsesquioxane/epoxy resin hybrid material
CN108441153A (en) * 2018-04-08 2018-08-24 湖州丘天电子科技有限公司 A kind of high-performance epoxy resin base electron pouring sealant and its preparation process
CN108659471A (en) * 2018-05-23 2018-10-16 北京化工大学 A kind of light-cured resin and preparation method thereof that polyfunctionality POSS is modified

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304960A (en) * 2013-05-23 2013-09-18 厦门大学 Preparation method of co-continuous POSS (Polyhedral Oligomeric Silsesquioxane)-epoxy modified resin
CN104845049A (en) * 2015-06-05 2015-08-19 厦门大学 Preparation method of phosphorus-containing flame-retardant organic-inorganic hybrid silsesquioxane/epoxy resin hybrid material
CN108441153A (en) * 2018-04-08 2018-08-24 湖州丘天电子科技有限公司 A kind of high-performance epoxy resin base electron pouring sealant and its preparation process
CN108659471A (en) * 2018-05-23 2018-10-16 北京化工大学 A kind of light-cured resin and preparation method thereof that polyfunctionality POSS is modified

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114539876A (en) * 2022-03-01 2022-05-27 高尧 Corrosion-resistant heat-dissipation protective coating and preparation method thereof
CN114806091A (en) * 2022-05-18 2022-07-29 陈全辉 POSS-CuPc-SiO 2 Preparation method of modified epoxy resin composite material

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