CN111234464A - Vacuum epoxy resin infusion system and preparation method and application thereof - Google Patents

Abstract

The invention provides a vacuum infusion epoxy resin system and a preparation method and application thereof. The invention provides a vacuum infusion epoxy resin system which is prepared by mixing a component A and a component B, wherein the component A comprises bisphenol A epoxy resin and an epoxy diluent, and the component B comprises a polyether amine curing agent and alicyclic amine; the epoxy diluent comprises polyepoxy tar containing cyclododecane structure, and optionally comprises other epoxy diluents.

Description

Vacuum epoxy resin infusion system and preparation method and application thereof

Technical Field

The invention relates to a formula of vacuum infusion epoxy resin for a wind power blade, in particular to a vacuum infusion epoxy resin system for a wind power blade, which has the advantages of good infusion, super-long operable time, high curing strength and temperature resistance.

Background

In the industrial production process of 1, 2-epoxy-5, 9-cyclododecadiene (ECDD), the main byproducts are diepoxide (DECD) and triepoxide (DECD) heavy component tar generated by the over-epoxidation of Cyclododecatriene (CDT), taking 1 ten thousand tons of ECDD devices as an example, the production amount of polyepoxide tar waste is 2000t/a (namely tons/year), and a special incinerator is required to be arranged in the normal production process for incineration treatment. If the epoxy tar can be effectively and comprehensively utilized, the ECDD production cost and the three-waste treatment pressure can be reduced, and a new product series can be developed by utilizing the special structure of macrocyclic polyepoxy.

Through gas chromatography-mass spectrometry, gas chromatography and atomic emission spectrometer detection, the tar is determined to have the components of 1, 2-epoxy-5, 9-cyclododecadiene (ECDD) 30%, 1,2,5, 6-diepoxy-9-cyclododecene 65% (DECD) and 1,2,5,6,9, 10-tricyclodecane oxide (TECD) 5%. The structure is as follows:

at present, more than 80 percent of wind power blades in the world are made of fiber reinforced composite materials produced by a vacuum auxiliary pouring process. When the composite material blades with the length of more than 30 meters are produced, the vacuum resin infusion system is required to have the characteristics of medium viscosity, long operable time and high curing strength, and at present, the problems of composite material defects caused by high epoxy resin curing speed and short operation time are often encountered in the production of common resin infusion systems in the market.

Disclosure of Invention

The invention provides a vacuum infusion epoxy resin system, wherein the raw material of the used epoxy diluent comprises polyepoxy tar containing a cyclododecane structure, and the vacuum infusion epoxy resin system can obtain more than medium initial mixing viscosity, lower exothermic peak temperature and longer operability time.

In order to achieve the purpose, the invention provides the following technical scheme:

the invention provides a vacuum infusion epoxy resin system which is prepared by mixing a component A and a component B, wherein the component A comprises bisphenol A epoxy resin and an epoxy diluent, and the component B comprises a polyether amine curing agent and alicyclic amine; the epoxy diluent comprises polyepoxy tar containing cyclododecane structure, and optionally comprises other epoxy diluents.

In addition, compared with other vacuum epoxy resin pouring systems, the special epoxy resin added with the polyepoxy tar as the epoxy diluent has the advantages of multiple active sites, high mechanical strength of products, low reaction activity and long processing operation time.

In some embodiments, the polyepoxy tar is a mixture of compounds containing cyclododecane structures with functionalities of 1,2, and 3, respectively.

In some embodiments, the polyepoxy tar is a mixture of 1, 2-epoxy-5, 9-cyclododecadiene, 1,2,5, 6-diepoxy-9-cyclododecene, and 1,2,5,6,9, 10-tricyclocyclododecane;

in some embodiments, the polyepoxy tar comprises the following components in percentage by weight: 10 to 40 percent of 1, 2-epoxy-5, 9-cyclododecadiene, 57 to 80 percent of 1,2,5, 6-diepoxy-9-cyclododecene and 3 to 10 percent of 1,2,5,6,9, 10-tricyclocyclododecane.

Specifically, the polyepoxy tar containing the cyclododecane structure is polyepoxy tar which is a byproduct in an ECDD industrial production process, and typical tar compositions are 1, 2-epoxy-5, 9-cyclododecadiene 30%, 1,2,5, 6-diepoxy-9-cyclododecene 65%, and 1,2,5,6,9, 10-tricyclodecane 5%.

The polyepoxy tar introduced as a byproduct in the industrial ECDD production process has an active epoxy structure, multiple functionality and low viscosity, and is latent as an epoxy diluent. Not only can reduce the viscosity of a resin system, but also can improve the crosslinking degree of the epoxy resin and the mechanical strength of the resin.

Aiming at the problems of a large amount of polyepoxy tar generated in the ECDD production process and the defects of the existing vacuum resin infusion system technology, the polyepoxy tar is skillfully introduced into the vacuum resin infusion system as an epoxy diluent, industrial wastes are comprehensively recycled to prepare the special epoxy diluent for the wind power blade, and some problems in the prior art are solved.

According to the vacuum epoxy resin infusion system provided by the invention, the raw material of the epoxy diluent can be tar generated in the ECDD production process, industrial byproducts are fully utilized, and the vacuum epoxy resin infusion system has the advantages of environmental friendliness, excellent performance and the like.

In some embodiments, the A component comprises, in weight percent, 70-90% of the bisphenol A type epoxy resin, 10% -30% of the polyepoxy tar, and 0% -10% of the other epoxy diluent; the component B comprises 50-90% of the polyether amine curing agent and 10-50% of the alicyclic amine in percentage by weight; and the weight ratio of the component A to the component B is 100: (25-35) the preferred component ratios are used to facilitate lower peak exothermic temperatures and longer run times while having more than moderate initial mix viscosities.

In some embodiments, the bisphenol A type epoxy resin is selected from one or more of E-55(616), E-51(618), E-44(6101), E-42(634), E-35(637), E-20(601), E-12(604), E-06(607), E-03 (609); preferably one or more of E-55(616), E-51(618), E-44 (6101).

The epoxy diluent in the invention can be independently composed of polyepoxy tar generated in the ECDD production process or compounded with other common epoxy diluents. In some embodiments, the additional epoxy diluent is selected from alkylene glycidyl ethers, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, fatty glycidyl ethers, benzyl glycidyl ether, 1, 6-hexanediol diglycidyl ether; one or more of butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, and phenyl glycidyl ether are preferable.

Preferably, the weight ratio of the polyepoxy tar to the other epoxy diluents in the epoxy diluent is 50: 50-100: 0.

In some embodiments, the polyetheramine curing agent is selected from polyetheramine curing agents having a functionality of 2, preferably selected from one or more of D230, D400, D2000, more preferably D230. Wherein D represents a functionality of 2 and 230 represents a molecular weight. Preferably D230.

In some embodiments, the cycloaliphatic amine is an amine-type compound comprising at least one cycloaliphatic group, such as a primary amine compound comprising one or two cyclohexyl, cycloheptyl, or cyclopentyl groups, or a combination thereof; for example from 1, 4-diaminocyclohexane, 4 '-diaminodicyclohexylmethane, 1, 3-diaminocyclopentane, 4' -diaminodicyclohexylsulfone, 1,3- (4,4 '-diamino-dicyclohexyl) propane, 2- (4, 4' -diamino-dicyclohexyl) propane, 3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, 3-aminomethyl-3, 3, 5-trimethylcyclohexylamine (isophoronediamine IPDA); more preferably 3-aminomethyl-3, 3, 5-trimethylcyclohexylamine (isophoronediamine IPDA).

In the invention, the viscosity of the mixed resin obtained by mixing the component A and the component B at 25 ℃ is 240-360 mPa.s; the exothermic peak temperature of 100g of the mixed resin in a 200ml paper cup is lower than 90 ℃ at the ambient temperature of 25 +/-1 ℃; the workable time of the mixed resin at 30 ℃ is 200 to 300 minutes (i.e., the time for the mixed resin viscosity to increase to 500 mpa.s).

Peak heat release: 100g of the mixed resin was placed in a 200ml paper cup at the exothermic peak temperature in units of ℃ at an ambient temperature of 25 ℃. + -. 1 ℃.

Viscosity at 25 ℃: measured by an ASTMD2983 viscometer;

the invention also provides a preparation method of the vacuum epoxy resin infusion system for the wind power blade, which comprises the following steps,

preparing a component A and a component B, mixing the component A and the component B (no special requirement on temperature, operation at room temperature), and stirring to obtain mixed resin;

wherein the preparation of the component A comprises the following steps: putting the components of the component A into a reaction kettle, and heating to 40-80 ℃; starting the stirrer, continuously stirring at the speed of 100-500 rpm for 10-30 minutes, stopping heating, and returning the reaction kettle to normal temperature to obtain the component A;

the preparation of the component B comprises the following steps: continuously stirring (for example, 30 minutes) all the materials in the component B under stirring at the rotating speed of 100-500 rpm, and turning off stirring to obtain the component B; the mixing process has no special requirement on temperature and can be carried out at room temperature.

The invention provides application of the vacuum epoxy resin pouring system in wind power blades.

The technical scheme provided by the invention has the following beneficial effects:

1) according to the invention, the byproduct tar of the ECDD device is used as the epoxy diluent in the vacuum epoxy resin infusion system, so that the industrial waste is recycled, the three-waste treatment cost of the ECDD production process is reduced, and meanwhile, the tar raw material is low in price, so that the vacuum infusion resin suitable for the wind power blade can be produced at low cost.

2) The vacuum infusion resin system provided by the invention has the initial mixing viscosity (240-360mPa.s at 25 ℃) of more than medium, the exothermic peak temperature of 100g of the mixed resin system in a 200ml paper cup at the ambient temperature of 25 +/-1 ℃ is lower than 90 ℃, and meanwhile, the vacuum infusion resin system has longer operable time (the time for increasing the mixing viscosity to 500mPa.s at 30 ℃ is 200-300 minutes).

3) The vacuum resin infusion system can ensure that the vacuum resin infusion system has proper flow speed in the production process of the wind power blade, and has longer operable time to adapt to high temperature and longer blades. .

Detailed Description

The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.

To ensure comparability of the reaction data, experiments were performed in the following examples using the same batch of polyepoxy tar. Actually measured tar composition (weight percentage): 30% of 1, 2-epoxy-5, 9-cyclododecadiene, 65% of 1,2,5, 6-diepoxy-9-cyclododecene, 5% of 1,2,5,6,9, 10-tricyclocyclododecane, and 5% of polyepoxy tar which is a byproduct of Wanhua chemical group EPO equipment.

Example 1:

a vacuum epoxy resin pouring system for wind power blades comprises a component A and a component B, wherein the component A comprises the following components in percentage by weight: 70% of bisphenol A type epoxy resin; 30% of epoxy diluent I (polyepoxy tar), 0% of epoxy diluent II;

the component B comprises the following components in percentage by weight: 50% of polyether amine curing agent and 50% of isophorone diamine;

the component A and the component B are mixed according to the weight ratio of 100: 25 in proportion.

The preparation method of the system comprises the following steps:

step one, preparing a component A:

putting bisphenol A type epoxy resin, an epoxy diluent I and an epoxy diluent II into a reaction kettle; heating the reaction kettle to 60 ℃, stirring at 100rpm for 30 minutes, and stopping; stopping heating, and cooling to normal temperature to obtain the component A;

step two, preparing a component B:

adding a polyether amine curing agent and isophorone diamine into a reaction kettle, stirring at 100rpm for 30 minutes, and stopping to obtain the component B;

and step three, mixing the prepared component A and the component B according to the weight part ratio, and stirring to obtain the composition.

Examples 2 to 7 and comparative example 1

The preparation methods of examples 2 to 7 and comparative example 1 are the same as those of example 1, and are not repeated herein, except for the composition in the ratio. The formulation of the vacuum infusion epoxy system of each example is shown in the following table:

comparative example 2: hexion, RIMTM R035c/RIM H037 vacuum infusion system.

Comparative example 3: the Dow chemical, 760E/766H vacuum infusion system of AIRSTONETM.

The vacuum infusion systems of the examples and comparative examples were evaluated for performance as shown in the following table.

Evaluation item	A/B ratio	A/B mixing viscosity/mPa.s	Operable time/min	Exothermic peak temperature/. degree.C
					Example 1	100/25	360	300	82
Example 2	100/30	330	280	83
					Example 3	100/30	280	250	85
Example 4	100/35	240	200	88
					Example 5	100/30	290	210	85
Example 6	100/30	330	200	90
					Example 7	100/30	360	280	83
Comparative example 1	100/30	260	50	120
					Comparative example 2	100/30	305	120	103
Comparative example 3	100/30	220	100	107

And (3) testing conditions are as follows:

mixing viscosity: 25 ℃, astm d2983 viscometer;

operable time: 30 ℃ rotational viscometer (THS-NDJ-5S), 200g of the mixed resin, the time required for the viscosity to increase to 500mPa.s, in min.

Exothermic peak temperature: 100g of the mixed resin was placed at the exothermic peak temperature in 200ml paper cups at 25 ℃.

It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.

Claims (10)

1. A vacuum infusion epoxy resin system is characterized in that the epoxy resin system is prepared by mixing a component A and a component B, wherein the component A comprises bisphenol A epoxy resin and an epoxy diluent, and the component B comprises a polyether amine curing agent and alicyclic amine; the epoxy diluent comprises polyepoxy tar containing cyclododecane structure, and optionally comprises other epoxy diluents.

2. The vacuum infusion epoxy resin system of claim 1, wherein the polyepoxy tar is a mixture of cyclododecane structure-containing compounds having functionalities of 1,2 and 3, respectively.

3. The vacuum infusion epoxy resin system of claim 1 or 2, wherein the polyepoxy tar is a mixture of 1, 2-epoxy-5, 9-cyclododecadiene, 1,2,5, 6-diepoxy-9-cyclododecene and 1,2,5,6,9, 10-tricyclocyclododecane;

preferably, the polyepoxy tar comprises the following components in percentage by weight: 10 to 40 percent of 1, 2-epoxy-5, 9-cyclododecadiene, 57 to 80 percent of 1,2,5, 6-diepoxy-9-cyclododecene and 3 to 10 percent of 1,2,5,6,9, 10-tricyclocyclododecane.

4. The vacuum infusion epoxy resin system of any one of claims 1-3, wherein the polyepoxy tar containing cyclododecane structure is derived from polyepoxy tar byproduct from ECDD industrial production process.

5. The vacuum infusion epoxy resin system of any one of claims 1-3, wherein said A component comprises, in weight percent, 70-90% of said bisphenol A type epoxy resin, 10% -30% of said polyepoxy tar, and 0% -10% of said other epoxy diluent;

the component B comprises 50-90% of the polyether amine curing agent and 10-50% of the alicyclic amine in percentage by weight;

and the weight ratio of the component A to the component B is 100: (25-35).

6. The vacuum infusion epoxy resin system of any one of claims 1-5, wherein the bisphenol a type epoxy resin is selected from one or more of E-55, E-51, E-44, E-42, E-35, E-20, E-12, E-06, E-03; preferably one or more of E-55, E-51, E-44;

and/or the further epoxy diluent is selected from alkylene glycidyl ethers, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, fatty glycidyl ethers, benzyl glycidyl ether, 1, 6-hexanediol diglycidyl ether; preferably one or more of butyl glycidyl ether, 1, 4-butanediol diglycidyl ether and phenyl glycidyl ether;

and/or the polyether amine curing agent is selected from polyether amine curing agents with the functionality of 2, preferably one or more selected from D230, D400 and D2000, and more preferably D230.

7. Vacuum infusion epoxy resin system according to any of the claims 1-6, wherein said cycloaliphatic amine is an amine compound comprising at least one cycloaliphatic group, such as a primary amine compound comprising one or two cyclohexyl, cycloheptyl or cyclopentyl groups or combinations thereof; preferably selected from 1, 4-diaminocyclohexane, 4 '-diaminodicyclohexylmethane, 1, 3-diaminocyclopentane, 4' -diaminodicyclohexylsulfone, 1,3- (4,4 '-diamino-dicyclohexyl) propane, 2- (4, 4' -diamino-dicyclohexyl) propane, 3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, 3-aminomethyl-3, 3, 5-trimethylcyclohexylamine (isophoronediamine IPDA); more preferably 3-aminomethyl-3, 3, 5-trimethylcyclohexylamine (isophoronediamine IPDA).

8. The vacuum infusion epoxy resin system of any one of claims 1-7, wherein the viscosity of the mixed resin obtained after mixing the A component and the B component is 240-360mPa.s at 25 ℃; the exothermic peak temperature of 100g of the mixed resin in a 200ml paper cup is lower than 90 ℃ at the ambient temperature of 25 +/-1 ℃; the workable time of the mixed resin at 30 ℃ is 200-300 minutes.

9. The method of preparing a vacuum infusion epoxy resin system as claimed in any one of claims 1 to 8, comprising the steps of,

preparing a component A and a component B, then mixing the component A and the component B, and stirring to obtain mixed resin;

wherein the preparation of the component A comprises the following steps: putting the components of the component A into a reaction kettle, heating to 40-80 ℃, and continuously stirring at the speed of 100-500 rpm for 10-30 minutes;

the preparation of the component B comprises the following steps: and (3) uniformly mixing all the materials in the component B under the stirring of the rotating speed of 100rpm-500rpm to obtain the component B.

10. Use of a vacuum infusion epoxy resin system as claimed in any one of claims 1 to 9 in fibre reinforced composites such as wind blades.