Preparation method of solvent-free liquid phosphorus-containing epoxy resin

Abstract

The invention discloses a preparation method of solvent-free liquid phosphorus-containing epoxy resin, which is characterized by comprising the following steps of: adding 5 to 60 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 5 to 60 parts by mass of diphenyl phosphine oxide (DPO), 55 to 100 parts by mass of aliphatic epoxy compound or alicyclic epoxy resin and 130 to 205 parts by mass of bisphenol diglycidyl ether into a reactor; the preparation method comprises the following steps: adding 0.09-0.45 part by mass of a catalyst into a reaction kettle, heating to 80-110 DEG C while stirring, keeping the temperature to react for 1.5-3.5 hours, adding 0.09-0.45 part by mass of a catalyst, reacting for 2-5 hours at 120-150 DEG C (heat preservation), heating to 160-190 DEG C (heat preservation) to react for 1-3 hours, cooling, and adding 1-5 parts by mass of novolac epoxy resin to obtain the solvent-free liquid phosphorus-containing epoxy resin. The liquid phosphorus-containing epoxy resin prepared by the invention is particularly suitable for being used as matrix resin of materials such as copper-clad plates, laminated plates, carbon fiber prepregs, winding coil pipe products and the like in a dry process.

Description

Technical Field

[0001] The invention belongs to the preparation of polymer compounds, and relates to a method for preparing a solvent-free liquid phosphorus-containing epoxy resin. The liquid phosphorus-containing epoxy resin prepared by the invention is particularly suitable for use as a matrix resin for materials such as copper-clad plates, laminates, carbon fiber prepregs, and winding tube products in a dry process. Background Art

[0002] In flame-retardant sheet and coil products, the main resin generally uses brominated epoxy resin, which makes the product flame-retardant through the action of bromine. Since the EU's RoHS and WEEE directives came into effect in 2003, environmentally friendly products have become a trend, and halogen-free flame retardancy has become a basic requirement in the copper clad laminate industry. As an important modified halogen-free flame-retardant matrix resin, phosphorus-containing epoxy resin is widely used in electronic copper clad laminates, laminates, inks, adhesives and various composite materials due to its halogen-free flame-retardant properties. Conventional phosphorus-containing epoxy resins generally use one or a mixture of butanone, acetone, and propylene glycol methyl ether as solvents. In subsequent production and processing, an oven is required to volatilize the solvent and an exhaust system is used for collection and treatment, which greatly increases the difficulty of the processing process, increases the manufacturing cost, and poses safety and environmental risks. Therefore, it is of great significance to develop environmentally friendly solvent-free liquid phosphorus-containing epoxy resins.

[0003] The existing preparation method of industrial phosphorus-containing epoxy resin mainly uses 9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide (DOPO for short) or its derivatives to react with various epoxy resins under the action of a catalyst to produce phosphorus-modified epoxy resins. The softening point of this type of resin is very high, generally exceeding 100°C, which is not convenient to use. In actual production, solvents are generally added to dissolve into 60%-80% resin solutions for use as finished products. However, the phosphorus-containing epoxy resin produced by this method is subject to many restrictions on use due to the presence of solvents, and some manufacturers are even unable to use this type of product because they do not have solvent-free qualifications. Therefore, under the development trend of safe and environmentally friendly materials, the design of solvent-free liquid phosphorus-containing epoxy resins is to meet the urgent requirements of solvent-free and halogen-free, and has important industrial application value. Summary of the invention

[0004] The purpose of the present invention is to overcome the deficiencies in the above-mentioned prior art and provide a method for preparing a solvent-free liquid phosphorus-containing epoxy resin. The present invention redesigns the product structure, uses 9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide (DOPO for short) or diphenylphosphine oxide (DPO) as a phosphorus source, and uses aliphatic epoxy compounds or alicyclic epoxy resins, phenolic epoxy resins, and bisphenol-type diglycidyl ether as raw materials, and is divided into two stages of reaction under the action of a catalyst to prepare a solvent-free liquid phosphorus-containing epoxy resin, thereby providing a method for preparing a solvent-free liquid phosphorus-containing epoxy resin with good product performance, halogen-free and environmentally friendly.

[0005] The content of the present invention is: a method for preparing a solvent-free liquid phosphorus-containing epoxy resin, characterized in that: 5 to 60 parts by weight of 9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide (DOPO), 5 to 60 parts by weight of diphenylphosphine oxide (DPO), 55 to 100 parts by weight of aliphatic epoxy compounds or alicyclic epoxy resins, and 130 to 205 parts by weight of bisphenol-type diglycidyl ether are added to a reactor, heated to 80°C to 110°C under stirring, kept at this temperature for reaction for 1.5 to 3.5 hours, then 0.09 to 0.45 parts by weight of a catalyst is added, reacted at a temperature of 120°C to 150°C (heat preservation) for 2 to 5 hours, then heated to 160°C to 190°C (heat preservation) for reaction for 1 to 3 hours, then cooled, and then 1 to 5 parts by weight of phenolic epoxy resin are added to obtain a solvent-free liquid phosphorus-containing epoxy resin;

[0006] The aliphatic epoxy compound or alicyclic epoxy resin may be one or a mixture of two of n-butyl glycidyl ether, methacrylate glycidyl ether, allyl glycidyl ether, diglycidyl ether, styrene oxide, phenyl glycidyl ether, diglycidyl aniline, and glycerol triglycidyl ether;

[0007] The catalyst can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, tetramethylammonium bromide and tetramethylammonium chloride.

[0008] In the content of the present invention: the bisphenol type diglycidyl ether can be one of bisphenol A type diglycidyl ether and bisphenol F type diglycidyl ether or a mixture of the two. The production and supply enterprises of bisphenol type diglycidyl ether include Nan Ya Plastic Industry Co., Ltd., Shandong Laiwu Runda New Materials Co., Ltd., Guodu Chemical (Kunshan) Co., Ltd., Shandong Aimonte New Materials Co., Ltd., etc.

[0009] In the content of the present invention: the novolac epoxy is phenol-type novolac epoxy. The production and supply enterprises of novolac epoxy include Nan Ya Plastic Industry Co., Ltd., Shandong Laiwu Runda New Materials Co., Ltd., Shandong Deyuan Epoxy Technology Co., Ltd., Shandong Aimonte New Materials Co., Ltd., etc.

[0010] In the content of the present invention: the physicochemical data of the solvent-free liquid phosphorus-containing epoxy resin solution are: viscosity 8000-15000 mPa·s, epoxy equivalent 180-260 g / eq, phosphorus content 2.0%-3.0%, molecular weight 200-500, glass transition temperature 130°C-145°C, and it is a light yellow to yellow transparent liquid.

[0011] The definition of "phosphorus content" in the present invention is: the percentage of phosphorus content in the total mass of phosphorus-containing epoxy resin.

[0012] Compared with the prior art, the present invention has the following characteristics and beneficial effects:

[0013] (1) The present invention uses an aliphatic epoxy compound or an alicyclic epoxy resin as a matrix and DOPO as a phosphorus source to prepare a matrix phosphorus-containing epoxy resin through an addition reaction. By reducing the molecular weight of the matrix phosphorus-containing epoxy resin, the softening point of the resin is reduced, making it a liquid phosphorus-containing epoxy resin that can flow, thereby greatly expanding its application field;

[0014] (2) The present invention introduces a multifunctional phenolic epoxy resin to increase the crosslinking density of the phosphorus-containing epoxy resin during curing while ensuring that the resin is flowable, thereby providing a solvent-free flowable phosphorus-containing epoxy resin while ensuring the flame retardancy and heat resistance of the product;

[0015] (3) The preparation process of the present invention is simple, and the obtained solvent-free liquid phosphorus-containing epoxy resin product has good performance, excellent heat resistance, flame retardancy and flexibility. It is an environmentally friendly flame retardant material with the characteristics of being environmentally friendly, easy to operate, and highly practical. DETAILED DESCRIPTION

[0016] The following embodiments are intended to further illustrate the present invention, but should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by technicians in this field based on the above-mentioned contents of the present invention still fall within the scope of protection of the present invention.

[0017] Embodiment 1:

[0018] A method for preparing a solvent-free liquid phosphorus-containing epoxy resin is as follows: 5kg DOPO, 45kg DPO, 60kg n-butyl glycidyl ether, 50kg bisphenol A epoxy 127, and 150kg bisphenol F epoxy 170 are added to a reactor, heated to 80°C under stirring, kept at this temperature for reaction for 1.5h, then 0.09kg catalyst imidazole is added, kept at 115°C for reaction for 4.5h, then heated to 160°C for reaction for 3h, then cooled to 130°C-140°C, and 5kg phenol novolac epoxy resin 638 is added to prepare a solvent-free liquid phosphorus-containing epoxy resin. The epoxy equivalent is 238.9g / mol, the phosphorus content is 2.9%, and the viscosity is 13890mpa.s.

[0019] Embodiment 2:

[0020] A method for preparing a solvent-free liquid phosphorus-containing epoxy resin is as follows: 30 kg DOPO, 30 kg DPO, 100 kg glycidyl methacrylate, 40 kg bisphenol A epoxy 127, and 90 kg bisphenol F epoxy 170 are added to a reactor, heated to 90° C. under stirring, kept at this temperature for 2 hours, then 0.25 kg catalyst 2-methylimidazole is added, kept at 110° C. for 5 hours, then heated to 170° C. for 3 hours, then cooled to 130° C. to 140° C., and 4 kg phenol novolac epoxy resin 638 is added to prepare a solvent-free liquid phosphorus-containing epoxy resin. The epoxy equivalent is 246.9 g / mol, the phosphorus content is 3.0%, and the viscosity is 9800 mPa.s.

[0021] Embodiment 3:

[0022] A method for preparing a solvent-free liquid phosphorus-containing epoxy resin comprises: adding 10 kg DOPO, 40 kg DPO, 90 kg allyl glycidyl ester, 30 kg bisphenol A epoxy 127, and 160 kg bisphenol F epoxy 170 into a reactor, heating to 95° C. under stirring, maintaining the temperature for reaction for 2.5 hours, then adding 0.33 kg catalyst triphenylphosphine, maintaining the temperature for reaction at 110° C. for reaction for 3 hours, then heating to 175° C. for reaction for 2.5 hours, then cooling to 130° C. to 140° C., adding 3 kg phenol novolac epoxy resin 638, and preparing a solvent-free liquid phosphorus-containing epoxy resin. The epoxy equivalent is 202.3 g / mol, the phosphorus content is 2.5%, and the viscosity is 12120 mPa.s.

[0023] Embodiment 4:

[0024] A method for preparing a solvent-free liquid phosphorus-containing epoxy resin is as follows: 43 kg DOPO, 15 kg DPO, 55 kg triglycidyl ether, 50 kg bisphenol A epoxy 127, and 130 kg bisphenol F epoxy 170 are added to a reactor, heated to 100° C. under stirring, kept at this temperature for 1 hour, then 0.23 kg of catalyst triphenyl phosphate is added, kept at 130° C. for 3.5 hours, then heated to 165° C. for 3 hours, then cooled to 130° C. to 140° C., and 2 kg of phenol novolac epoxy resin 638 are added to prepare a solvent-free liquid phosphorus-containing epoxy resin. The epoxy equivalent is 181.2 g / mol, the phosphorus content is 2.9%, and the viscosity is 14320 mPa.s.

[0025] Embodiment 5:

[0026] A method for preparing a solvent-free liquid phosphorus-containing epoxy resin is as follows: 7kg DOPO, 60kg DPO, 79kg styrene oxide, 40kg bisphenol A epoxy 127, and 152kg bisphenol F epoxy 170 are added to a reactor, heated to 90°C under stirring, kept at this temperature for 3h, then 0.15kg catalyst triethylbenzyl ammonium chloride is added, kept at 110°C for 2h, then heated to 180°C for 1.5h, then cooled to 130°C-140°C, and 3kg phenol novolac epoxy resin 638 is added to prepare a solvent-free liquid phosphorus-containing epoxy resin. The epoxy equivalent is 232.6g / mol, the phosphorus content is 3.0%, and the viscosity is 12790mpa.s.

[0027] Embodiment 6:

[0028] A method for preparing a solvent-free liquid phosphorus-containing epoxy resin is as follows: 60 kg DOPO, 5 kg DPO, 88 kg phenyl glycidyl ether, and 160 kg bisphenol F epoxy 170 are added to a reactor, heated to 85° C. under stirring, kept at this temperature for reaction for 3.5 hours, then 0.3 kg of catalyst tetrabutylammonium bromide is added, kept at 118° C. for reaction for 4 hours, then heated to 190° C. for reaction for 1 hour, then cooled to 130° C. to 140° C., and 1 kg of phenol novolac epoxy resin 638 is added to prepare a solvent-free liquid phosphorus-containing epoxy resin. The epoxy equivalent is 252.9 g / mol, the phosphorus content is 3.0%, and the viscosity is 11830 mPa.s.

[0029] Embodiment 7:

[0030] A method for preparing a solvent-free liquid phosphorus-containing epoxy resin is as follows: 11 kg DOPO, 50 kg DPO, 92 kg diglycidyl aniline, 15 kg bisphenol A epoxy 127, and 165 kg bisphenol F epoxy 170 are added to a reactor, heated to 100° C. under stirring, kept at the temperature for reaction for 2 hours, then 0.1 kg of catalyst tetramethylammonium chloride is added, kept at 105° C. for reaction for 2.5 hours, then heated to 185° C. for reaction for 1.5 hours, then cooled to 130° C. to 140° C., and 5 kg of phenol novolac epoxy resin 638 is added to prepare a solvent-free liquid phosphorus-containing epoxy resin. The epoxy equivalent is 200.0 g / mol, the phosphorus content is 2.7%, and the viscosity is 11350 mPa.s.

[0031] Embodiment 8:

[0032] A method for preparing a solvent-free liquid phosphorus-containing epoxy resin comprises: adding 21 kg DOPO, 55 kg DPO, 96 kg glycerol triglycidyl ether, 35 kg bisphenol A epoxy 127, and 170 kg bisphenol F epoxy 170 into a reactor, heating to 85° C. under stirring, maintaining the temperature for reaction for 1.5 hours, then adding 0.35 kg catalyst butyl triphenylphosphonium bromide, maintaining the temperature for reaction at 120° C. for 1.5 hours, then heating to 165° C. for reaction for 3 hours, then cooling to 130° C. to 140° C., adding 2 kg phenol novolac epoxy resin 638, and preparing a solvent-free liquid phosphorus-containing epoxy resin. The epoxy equivalent is 194.4 g / mol, the phosphorus content is 3.0%, and the viscosity is 10800 mPa.s.

[0033] In the above embodiments: the percentages used, unless otherwise specified, are all mass (weight) percentages or percentages known to those skilled in the art; the proportions used, unless otherwise specified, are all mass (weight) proportions; and the mass (weight) parts are all grams or kilograms.

[0034] In the above embodiments, the process parameters (temperature, time, etc.) in each step and the numerical values ​​of the amounts of each component are ranges, and any point can be applied.

[0035] The technical contents not specifically described in the present invention and the above embodiments are the same as the prior art, and the raw materials are all commercially available products.

[0036] The present invention is not limited to the above embodiments, and all of the contents of the present invention can be implemented and have the above good effects.

Claims

1. A method for preparing a solvent-free liquid phosphorus-containing epoxy resin, characterized in that: 5 to 60 parts by weight of 9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide (DOPO), 5 to 60 parts by weight of diphenylphosphine oxide (DPO), 55 to 100 parts by weight of aliphatic epoxy compounds or alicyclic epoxy resins, and 130 to 205 parts by weight of bisphenol-type diglycidyl ether are added into a reactor, heated to 80 to 110° C. under stirring, and kept at this temperature for reaction for 1.5 to 3.5 hours, then 0.09 to 0.45 parts by weight of a catalyst is added, and the reaction is carried out at a temperature of 120 to 150° C. (keeping temperature) for 2 to 5 hours, and then the temperature is raised to 160 to 190° C. (keeping temperature) for reaction for 1 to 3 hours, and then cooled, and then 1 to 5 parts by weight of a novolac epoxy resin is added to obtain a solvent-free liquid phosphorus-containing epoxy resin.

2. The aliphatic epoxy compound or alicyclic epoxy resin according to claim 1 can be one or a mixture of two of n-butyl glycidyl ether, methacrylate glycidyl ether, allyl glycidyl ether, diglycidyl ether, styrene oxide, phenyl glycidyl ether, diglycidyl aniline, and glycerol triglycidyl ether.

3. The bisphenol diglycidyl ether according to claim 1 can be one of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether or a mixture of both.

4. The catalyst according to claim 1 can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, tetramethylammonium bromide and tetramethylammonium chloride.

5. The novolac epoxy according to claim 1 is a phenol-type novolac epoxy.

6. The physicochemical data of the solvent-free liquid phosphorus-containing epoxy resin solution prepared according to claim 1 are as follows: viscosity 8000-15000 mPa·s, epoxy equivalent 180-260 g / eq, phosphorus content 2.0%-3.0%, molecular weight 200-500, glass transition temperature 130°C-145°C, and it is a light yellow to yellow transparent liquid.