阅读说明：本技术 一种高模量杂环环氧树脂的制备方法 (Preparation method of high-modulus heterocyclic epoxy resin ) 是由 李文泉 李冉 李文峰 于 2020-12-24 设计创作，主要内容包括：本发明公开了一种高模量杂环环氧树脂的制备方法。本发明采用苯三酚与烯丙基氯反应生成1-烯丙基苯三酚,高温转位,环合得到杂环双酚,杂环双酚与环氧氯丙烷在液碱的催化作用下进行反应,然后溶剂精制,得到一种杂环环氧树脂。该杂环环氧树脂固化后具有很高的模量,粘接性,耐候性,与普通的环氧树脂混合具有很好的相容性,可以改善环氧树脂的整体性能。(The invention discloses a preparation method of high-modulus heterocyclic epoxy resin. The invention adopts the technical scheme that benzene trisphenol and allyl chloride react to generate 1-allyl benzene trisphenol, heterocyclic bisphenol is obtained through high-temperature transposition and cyclization, the heterocyclic bisphenol and epoxy chloropropane react under the catalysis of liquid alkali, and then solvent refining is carried out, so as to obtain the heterocyclic epoxy resin. The heterocyclic epoxy resin has high modulus, adhesiveness and weather resistance after being cured, has good compatibility when being mixed with common epoxy resin, and can improve the overall performance of the epoxy resin.)

1. The preparation method of the high-modulus heterocyclic epoxy resin is characterized by comprising the following steps of:

1) the benzene triphenol reacts with allyl chloride to generate 1-allyl benzene triphenol;

2) under the catalysis of a catalyst, performing high-temperature transposition on 1-allyl benzenetriol under negative pressure, and performing cyclization to obtain heterocyclic bisphenol;

3) and (3) reacting the heterocyclic bisphenol with epoxy chloropropane under the catalytic action of liquid alkali to obtain the heterocyclic epoxy resin.

2. The process for preparing a high modulus heterocyclic epoxy resin as claimed in claim 1, wherein said benzenetriol is 1,2, 3-benzenetriol, 1,3, 5-benzenetriol or 1,2, 4-benzenetriol.

3. The process for preparing a high modulus heterocyclic epoxy resin as claimed in claim 1, wherein the reaction temperature of step 1) is 55-60 ℃.

4. The preparation method of high modulus heterocyclic epoxy resin as claimed in claim 1, wherein the high temperature of step 2) is 250-260 ℃, and the negative pressure is: the negative pressure is 0.4 MPa.

5. The process for preparing high modulus heterocyclic epoxy resin as claimed in claim 1, wherein said catalyst of step 2) is aluminum trichloride or nano vanadium salt.

6. The process for preparing a high modulus heterocyclic epoxy resin as claimed in claim 1, wherein said step 3) is specifically: heating and dissolving heterocyclic bisphenol and epoxy chloropropane, adding liquid alkali at 1, 55-60 ℃ for reaction for 2-3h, continuously heating to 78-80 ℃, adding liquid alkali 2, and continuously keeping the temperature for reaction for 4-5 h.

7. The process for preparing high modulus heterocyclic epoxy resin according to claim 6, characterized in that the liquid alkali 1 is sodium hydroxide or potassium hydroxide in an amount of 18-22% by mass of epichlorohydrin, and the liquid alkali 2 is sodium hydroxide or potassium hydroxide in an amount of 50% by mass of epichlorohydrin in an amount of 40-50% by mass of epichlorohydrin.

8. The process for the preparation of the high modulus heterocyclic epoxy resin of any one of claims 1 to 7 comprising the steps of:

1) adding 1,2, 4-benzenetriol and allyl chloride into a reaction container, and stirring and reacting for 2-5h at the temperature of 55-60 ℃;

2) then adding catalyst aluminum trichloride, heating to 250-260 ℃, generating transposition and cyclization for 1-2h under the negative pressure of 0.4MPa, washing with water, and drying to obtain heterocyclic bisphenol;

3) heating heterocyclic bisphenol and epoxy chloropropane to fully dissolve, continuously heating to 55-60 ℃, introducing 30% sodium hydroxide or potassium hydroxide solution, keeping the temperature and reacting for 2-3h, continuously adding 50% sodium hydroxide or potassium hydroxide solution, heating to 78-80 ℃, keeping the temperature and reacting for 4-5h, washing, adding acetone, toluene or xylene for extraction, and removing the solvent by concentration under reduced pressure to obtain the high-modulus heterocyclic epoxy resin.

9. The high modulus heterocyclic epoxy resin prepared by the process of claim 8.

Technical Field

The invention belongs to the technical field of new materials, and relates to a preparation method of high-modulus heterocyclic epoxy resin.

Background

The epoxy resin is a generic name of a polymer having two or more epoxy groups in a molecule. The epoxy resin can be crosslinked with amine or anhydride curing agents to form insoluble and infusible polymers with three-dimensional network structures. The excellent physical mechanical and electrical insulation properties of epoxy resins, their adhesion to various materials, and their flexibility in the process of use are not available with other thermosets. Therefore, the material can be made into coating, composite materials, casting materials, adhesives, mould pressing materials and injection molding materials, and can be widely applied to various fields of national economy.

The epoxy resin has excellent mechanical property and bonding property, but has poor weather resistance, and can be brittle, peeled, cracked and the like in less than two to three years particularly in western outdoor areas. The common solution in the market at present is to add an anti-ultraviolet filler into an epoxy resin and curing agent system, which is inconvenient to operate, and often requires an organic solvent to adjust the viscosity, and the generation of VOCs causes great pressure to the environment. Meanwhile, even if the ultraviolet resistance of the composite material is improved by adding the filler, the composite material has difficulty in balancing good bending modulus and ultraviolet resistance.

Aiming at the problems, the invention synthesizes heterocyclic bisphenol, heterocyclic bisphenol and epoxy chloropropane form heterocyclic epoxy resin under the action of liquid alkali, and the resin has high modulus, weather resistance and bonding property after being cured.

Disclosure of Invention

Aiming at the problems, the invention provides a preparation method of high-modulus heterocyclic epoxy resin. The invention adopts benzene triphenol and allyl chloride to react to generate 1-allyl benzene triphenol, carries out high-temperature transposition and cyclization to obtain heterocyclic bisphenol, and then carries out reaction on the heterocyclic bisphenol and epoxy chloropropane under the catalysis of liquid alkali, and then carries out solvent refining to obtain the heterocyclic epoxy resin. The epoxy resin has high modulus, adhesiveness and weather resistance after being cured, has good compatibility when being mixed with common epoxy resin, and can improve the overall performance of the epoxy resin.

The technical scheme of the invention is as follows: a preparation method of high modulus heterocyclic epoxy resin is characterized in that,

1) the benzene triphenol reacts with allyl chloride to generate 1-allyl benzene triphenol;

2) under the catalysis of a catalyst, performing high-temperature transposition on 1-allyl benzenetriol under negative pressure, and performing cyclization to obtain heterocyclic bisphenol;

3) and (3) reacting the heterocyclic bisphenol with epoxy chloropropane under the catalytic action of liquid alkali to obtain the heterocyclic epoxy resin.

The reaction equation is shown below.

Wherein the benzenetriol is 1,2, 3-benzenetriol, 1,3, 5-benzenetriol or 1,2, 4-benzenetriol, and preferably 1,2, 4-benzenetriol.

The reaction temperature of the step 1) is 55-60 ℃. The molar ratio of the benzene triphenol to the allyl chloride is 1 (0.95-1.05), and preferably 1: 1.

The reaction temperature in the step 2) is 250-260 ℃, and the negative pressure is as follows: the negative pressure is 0.4 MPa.

The catalyst in the step 2) is aluminum trichloride, nano vanadium salt and the like, and the catalyst can lead phenolic hydroxyl on a benzene ring and allyl chloride to generate transposition and cyclization reactions so as to obtain the expected heterocyclic phenol. The molar ratio of the benzenetriol to the catalyst is 1 (0.0001-0.005), preferably 1: 0.0005.

The step 3) is specifically as follows: heating and dissolving heterocyclic bisphenol and epoxy chloropropane, adding liquid alkali at 1, 55-60 ℃ for reaction for 2-3h, continuously heating to 78-80 ℃, adding liquid alkali 2, and continuously keeping the temperature for reaction for 4-5 h.

Wherein, the mass ratio of the heterocyclic bisphenol to the epichlorohydrin is 1 (0.95-1.05), preferably 1: 1.

wherein, the liquid alkali 1 is 30 percent of sodium hydroxide or potassium hydroxide, the dosage of which is 18 to 22 percent of the mass of the epichlorohydrin, and the liquid alkali 2 is 50 percent of sodium hydroxide or potassium hydroxide, the dosage of which is 40 to 50 percent of the mass of the epichlorohydrin.

Further, the method comprises the following specific steps:

1) adding 1,2, 4-benzenetriol and allyl chloride into a reaction container, and stirring and reacting for 2-5h at the temperature of 55-60 ℃;

2) then adding catalyst aluminum trichloride, heating to 250-260 ℃, generating transposition and cyclization for 1-2h under the negative pressure of 0.4MPa, washing with water, and drying to obtain heterocyclic bisphenol;

3) heating heterocyclic bisphenol and epoxy chloropropane to fully dissolve, continuously heating to 55-60 ℃, introducing 30% sodium hydroxide or potassium hydroxide solution, keeping the temperature and reacting for 2-3h, continuously adding 50% sodium hydroxide or potassium hydroxide solution, heating to 78-80 ℃, keeping the temperature and reacting for 4-5h, washing, adding acetone, toluene or xylene for extraction, and removing the solvent by concentration under reduced pressure to obtain the heterocyclic epoxy resin.

The invention has the beneficial effects that:

1) after being cured, the heterocyclic epoxy resin prepared by the method has high modulus, adhesiveness and weather resistance, has good compatibility when being mixed with common epoxy resin, and can improve the overall performance of the epoxy resin;

2) the preparation method is simple and suitable for industrial production.

Detailed Description

Example 1: preparation of high modulus heterocyclic epoxy resin

1) Adding 126g of 1,2, 4-benzenetriol and 76.5g of allyl chloride into a 500ml four-neck flask with a heating jacket, a stirrer and a reflux condenser, and stirring and reacting for 3 hours at the temperature of 55-60 ℃;

2) then adding 0.0665g of catalyst aluminum trichloride, heating to 250 ℃, carrying out transposition and cyclization for 80min under the negative pressure of 0.4MPa, washing for 3 times, and drying to obtain 152g of heterocyclic bisphenol;

3) weighing 100g of heterocyclic bisphenol and 100g of epichlorohydrin, heating to 30 ℃ for fully dissolving, continuously heating to 55 ℃, introducing 20g of 30% sodium hydroxide solution, keeping the temperature for reaction for 2 hours, continuously adding 46g of 50% sodium hydroxide solution, heating to 78 ℃, keeping the temperature for reaction for 4 hours, washing for 3 times, adding acetone for extraction for 3 times, 200ml each time, combining extract liquor, and removing the solvent through concentration under reduced pressure to obtain the heterocyclic epoxy resin.

Test example:

mechanical properties of cured products obtained by curing the heterocyclic epoxy resin obtained by the above method and the general epoxy resin E-44 (as a control) with a T31 curing agent at room temperature in parts by weight shown in Table 1 are shown in Table 1. Wherein, the bending test sample is prepared and tested according to the requirements of GB/T9341-2008 'determination of plastic bending performance', and the ultraviolet fatigue resistance test refers to the GB/T16422.3-2014 laboratory light source exposure test method. The test results are shown in table 1.

TABLE 1 mechanical Properties of cured products of ordinary epoxy resin E-44 and the heterocyclic epoxy resin with T31 curing agent

E-44 (in parts)	Heterocyclic epoxy resin (part)	T31 (in weight)	Flexural modulus (MPa)	Ultraviolet fatigue test (year)
					100	0	40	2.80	2.8
50	50	40	2.96	4.5
					0	100	40	3.20	6.3

As can be seen from table 1: after the heterocyclic epoxy resin prepared by the invention and a T31 curing agent are cured, compared with the common epoxy resin E-44, the bending modulus is improved by 14%, and the weather resistance time of an ultraviolet fatigue resistance test is improved by 125%. Therefore, the epoxy resin can be used as a substitute of the common epoxy resin E-44, and is particularly suitable for special environments with weather resistance requirements. The heterocyclic epoxy resin has good compatibility when mixed with common epoxy resin, and can be doped into the common epoxy resin to improve the overall performance of the epoxy resin.

Example 2: preparation of high modulus heterocyclic epoxy resin condensate

1) Adding 126g of 1,2, 3-benzenetriol and 77g of allyl chloride into a 500ml four-neck flask with a heating jacket, a stirrer and a reflux condenser, and stirring and reacting for 2.5h at the temperature of 55-60 ℃;

2) then adding 0.08g of catalyst aluminum trichloride, heating to 260 ℃, carrying out transposition and cyclization for 1.5h under the negative pressure of 0.4MPa, washing for 3 times, and drying to obtain 151g of heterocyclic bisphenol;

3) weighing 100g of heterocyclic bisphenol and 100g of epichlorohydrin, heating to 30 ℃ for fully dissolving, continuously heating to 58 ℃, introducing 22g of 30% sodium hydroxide solution, keeping the temperature for reaction for 1.5h, continuously adding 45g of 50% sodium hydroxide solution, heating to 80 ℃, keeping the temperature for reaction for 3.5h, washing with water for 3 times, adding toluene for extraction for 3 times, 200ml each time, combining extract liquor, and removing the solvent through concentration under reduced pressure to obtain the heterocyclic epoxy resin.

Example 3: preparation of high modulus heterocyclic epoxy resin condensate

1) Adding 126g of 1,3, 5-benzenetriol and 77g of allyl chloride into a 500ml four-neck flask with a heating jacket, a stirrer and a reflux condenser, and stirring and reacting for 2.5h at the temperature of 55-60 ℃;

2) then adding 0.07g of catalyst aluminum trichloride, heating to 260 ℃, carrying out transposition and cyclization for 1.5h under the negative pressure of 0.4MPa, washing for 3 times, and drying to obtain 151g of heterocyclic bisphenol;

3) weighing 100g of heterocyclic bisphenol and 100g of epichlorohydrin, heating to 30 ℃ for fully dissolving, continuously heating to 58 ℃, introducing 20g of 30% sodium hydroxide solution, keeping the temperature for reaction for 1.5h, continuously adding 45g of 50% sodium hydroxide solution, heating to 80 ℃, keeping the temperature for reaction for 3.5h, washing with water for 3 times, adding xylene for extraction for 3 times, 200ml each time, combining extract liquor, and removing the solvent by concentration under reduced pressure to obtain the heterocyclic epoxy resin.