CN111117157A - High-temperature-resistant hydrolysis-resistant epoxy resin matrix for sucker rod - Google Patents
High-temperature-resistant hydrolysis-resistant epoxy resin matrix for sucker rod Download PDFInfo
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- CN111117157A CN111117157A CN201911287760.4A CN201911287760A CN111117157A CN 111117157 A CN111117157 A CN 111117157A CN 201911287760 A CN201911287760 A CN 201911287760A CN 111117157 A CN111117157 A CN 111117157A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to the field of polymer chemical industry, and particularly provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod and a preparation method thereof. The invention provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod, which comprises a component A and a component B as preparation raw materials; the component A comprises bisphenol A epoxy resin, phenolic novolac Novolak epoxy resin, alicyclic epoxy resin and glycidyl amine epoxy resin; the component B comprises a curing agent, a toughening agent, an accelerant and a catalyst; the bisphenol A epoxy resin has an epoxy equivalent of 130 to 300 g/mol.
Description
Technical Field
The invention relates to the field of polymer chemical industry, and particularly provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod and a preparation method thereof.
Background
The sucker rod is used as an important component in the oil and gas industry, plays a key role in oil extraction operation, and influences the oil extraction efficiency and the oil extraction capacity. Along with the gradual deepening of the oil extraction depth of the oil field, the requirements on the self weight, the mechanical property, the temperature resistance and the corrosion resistance of the sucker rod are also gradually improved.
In order to solve the problems of low strength-weight ratio and poor corrosion resistance of the metal sucker rod, a composite sucker rod based on carbon fiber/epoxy resin is developed in the industry. The composite material sucker rod is produced by a pultrusion process, and has very high mechanical strength and modulus in the 0-degree direction. Meanwhile, the acid corrosion resistance is obviously higher than that of metal. According to the difference of oil extraction depth, the vitrification temperature of an epoxy pultrusion system for producing the composite material sucker rod is in two grades, namely the vitrification temperature is 110-130 ℃ and 160-180 ℃.
The epoxy pultrusion system of the composite material sucker rod used in the industry at present is mainly an epoxy resin-anhydride curing agent system, and because the working environment of the sucker rod is under the conditions of high pressure, high temperature and high humidity, the high requirement is also provided for the aging resistance of the epoxy pultrusion system under the conditions of high pressure, high temperature and high humidity. At present, many existing pultrusion systems are easy to decompose resin after being aged at high pressure, high temperature and high humidity, and the long-term reliability of the carbon fiber composite sucker rod is seriously influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod in a first aspect, and the preparation raw materials comprise a component A and a component B; the component A comprises bisphenol A epoxy resin, phenolic novolac Novolak epoxy resin, alicyclic epoxy resin and glycidyl amine epoxy resin;
the component B comprises a curing agent, a toughening agent, an accelerant and a catalyst;
the bisphenol A epoxy resin has an epoxy equivalent of 130 to 300 g/mol.
According to a preferable technical scheme of the invention, the component A comprises, by weight, 40-80 parts of bisphenol A epoxy resin, 10-30 parts of novolac Novolak epoxy resin, 5-30 parts of alicyclic epoxy resin and 0-100 parts of glycidylamine epoxy resin;
the component B comprises 30-120 parts of curing agent, 1-30 parts of toughening agent, 0-10 parts of accelerant and 0-10 parts of catalyst.
According to a preferable technical scheme, the component A comprises 50-70 parts by weight of bisphenol A epoxy resin, 15-25 parts by weight of phenolic novolac Novolak epoxy resin, 10-25 parts by weight of alicyclic epoxy resin and 30-70 parts by weight of glycidylamine epoxy resin;
the component B comprises 50-100 parts of curing agent, 5-20 parts of toughening agent, 1-5 parts of accelerant and 1-5 parts of catalyst.
As a preferable technical scheme of the invention, the epoxy equivalent of the bisphenol A type epoxy resin is 170-200 g/mol.
As a preferred technical solution of the present invention, the novolac type novolaks epoxy resin is selected from one or a combination of several of phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, and biphenol novolac epoxy resin.
As a preferred technical scheme of the invention, the accelerator is an imidazole accelerator.
As a preferable technical scheme of the invention, the imidazole accelerator is one or a combination of more of 1-methylimidazole, 2-phenylimidazole, dimethylbenzylamine, 1 benzyl 2-methylimidazole, 2 ethyl 4-methylimidazole, 1 cyanoethyl 2-phenylimidazole, 2 undecylimidazole and 1 cyanoethyl 2-methylimidazole.
As a preferred technical scheme of the invention, the curing agent is selected from one or a combination of several of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride and methyl nadic anhydride.
As a preferred technical scheme of the invention, the catalyst comprises a metal catalyst and a quaternary ammonium salt catalyst.
The second aspect of the invention provides a preparation method of the high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod, which at least comprises the following steps: and uniformly mixing the component A and the component B to obtain the composition.
Has the advantages that: the invention provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod, which can obtain viscosity suitable for a pultrusion process by regulating and controlling the type and parameters of added epoxy resin, can meet the high-level temperature-resistant requirement of the oil extraction industry, has better high-pressure-resistant high-humidity-resistant aging performance, is not easy to crack, and is suitable for a carbon fiber composite sucker rod.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the technical problems, the invention provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod in a first aspect, and the preparation raw materials comprise a component A and a component B; the component A comprises bisphenol A epoxy resin, phenolic novolac Novolak epoxy resin, alicyclic epoxy resin and glycidyl amine epoxy resin;
the component B comprises a curing agent, a toughening agent, an accelerant and a catalyst;
the bisphenol A epoxy resin has an epoxy equivalent of 130 to 300 g/mol.
In a preferred embodiment, the epoxy resin matrix for the sucker rod with high temperature resistance and hydrolysis resistance comprises, by weight, 40-80 parts of bisphenol A epoxy resin, 10-30 parts of novolac Novolac epoxy resin, 5-30 parts of alicyclic epoxy resin and 0-100 parts of glycidylamine epoxy resin;
the component B comprises 30-120 parts of curing agent, 1-30 parts of toughening agent, 0-10 parts of accelerant and 0-10 parts of catalyst.
In a more preferred embodiment, the epoxy resin matrix for the sucker rod with high temperature and hydrolysis resistance comprises, by weight, 50-70 parts of bisphenol A epoxy resin, 15-25 parts of novolac Novolac epoxy resin, 10-25 parts of alicyclic epoxy resin and 30-70 parts of glycidylamine epoxy resin;
the component B comprises 50-100 parts of curing agent, 5-20 parts of toughening agent, 1-5 parts of accelerant and 1-5 parts of catalyst.
In a more preferred embodiment, the epoxy resin matrix for sucker rod with high temperature and hydrolysis resistance comprises, by weight, 60 parts of bisphenol A epoxy resin, 20 parts of novolac Novolac epoxy resin, 17 parts of alicyclic epoxy resin and 50 parts of glycidylamine epoxy resin;
the component B comprises 75 parts of curing agent, 12 parts of toughening agent, 3 parts of accelerant and 3 parts of catalyst.
<Bisphenol A epoxy resin>
The bisphenol A type epoxy resin is a high molecular compound prepared by condensing bisphenol A and epoxy chloropropane under an alkaline condition, washing with water, and removing a solvent.
In one embodiment, the bisphenol A epoxy resin has an epoxy equivalent weight of 130 to 300 g/mol; more preferably, the bisphenol A type epoxy resin has an epoxy equivalent weight of 170-200 g/mol, and is purchased from Shandong de source epoxy technology Co., Ltd, and the type is DY-128E.
<Phenolic novolaks epoxy resins>
The phenolic novolac type Novolak epoxy resin is selected from one or a combination of a plurality of phenol novolac epoxy resin, o-cresol novolac epoxy resin and diphenol novolac epoxy resin.
In a preferred embodiment, the novolac type novolacs epoxy resin comprises a diphenolic novolac epoxy resin and an o-cresol novolac epoxy resin.
In a more preferred embodiment, the o-cresol novolac epoxy resin has an epoxy equivalent of 200 to 240g/mol, and is available from Vast chemical Co., Ltd., USA, as EPIKOTE 678.
In a more preferred embodiment, the mass ratio of the diphenol aldehyde epoxy resin to the o-cresol novolac epoxy resin is (1.5-2): 1; more preferably, the mass ratio of the diphenol aldehyde epoxy resin to the o-cresol novolac epoxy resin is 1.7: 1.
the raw materials for preparing the diphenol aldehyde epoxy resin comprise diphenol aldehyde and epoxy chloropropane.
In a preferred embodiment, the molar ratio of biphenyl phenol formaldehyde to epichlorohydrin is 1: (7-9); preferably, the molar ratio of the biphenyl phenol aldehyde to the epichlorohydrin is 1: 8.
in a preferred embodiment, the starting materials for the preparation of the diphenolaldehyde comprise 4, 4' -dimethoxymethylbiphenyl and phenol.
In a more preferred embodiment, the molar ratio of 4, 4' -dimethoxymethylbiphenyl to phenol is 1: (4-6); more preferably, the molar ratio of the 4, 4' -dimethoxymethylbiphenyl to the phenol is 1: 5.
in a more preferred embodiment, the process for the preparation of the diphenolaldehyde comprises: adding 4, 4' -dimethoxymethylbiphenyl and phenol into a 250mL four-mouth bottle, adding oxalic acid to adjust the pH value to 5-6, stirring and refluxing for reaction for 3-5 h under the nitrogen atmosphere, then heating to 180-190 ℃, and removing the redundant phenol by reduced pressure stirring to obtain the compound.
In a more preferred embodiment, the diphenolaldehyde epoxy resin is prepared by the process of: 20g of biphenyl phenol formaldehyde, 40g of epichlorohydrin and 3g of quaternary ammonium salt are sequentially added into a 250mL four-mouth bottle provided with an electric stirrer, a thermometer, a reflux condenser tube and a dropping funnel, heated and stirred to 65 ℃, and kept warm for 30 min. Then, 3.90g of 50 wt% NaOH solution was slowly added dropwise, the reaction was carried out for 2 hours, and the organic phase was separated by washing with water and then subjected to reduced pressure removal of epichlorohydrin. The resulting product was dissolved in methyl isobutyl ketone, and 0.650g of a 20 wt% NaOH solution was added thereto, followed by purification at 85 ℃ for 2 hours. And after the reaction is finished, washing with water until the pH value of the methyl isobutyl ketone solution is 7, and removing the methyl isobutyl ketone and the water by rotary evaporation to obtain the product.
The applicant has found that the added diphenolaldehyde epoxy resin can improve the high temperature and hydrolysis aging resistance of the system, which is probably because the diphenolaldehyde epoxy resin contains more hydrophobicity and stable chemical structure. However, when more o-phenol novolac epoxy resin is added, the phenomena of large brittleness, easy cracking and reduced hydrolysis and aging resistance are easy to occur, and when the mass ratio of the biphenyl novolac epoxy resin to the o-cresol novolac epoxy resin is controlled to be (1.5-2): 1, the high temperature resistance, hydrolysis resistance and aging resistance of the system can be greatly improved on the basis of not influencing the toughness of the system.
<Cycloaliphatic epoxy resins>
The epoxy equivalent of the alicyclic epoxy resin is 180-220 g/mol.
In a preferred embodiment, the cycloaliphatic epoxy resin is selected from one or a combination of bis ((3, 4-epoxycyclohexyl) methyl) adipate, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate, 3-ethyl-3-epoxypropanemethanol, dicyclopentadiene epoxide.
In a preferred embodiment, the cycloaliphatic epoxy resin is a bis ((3, 4-epoxycyclohexyl) methyl) adipate cycloaliphatic epoxy resin available from Jiningminda New materials, Inc. under model number RE 26.
In the experimental process, the applicant finds that when the epoxy equivalent of the bisphenol A epoxy resin is 170-190 g/mol, the curing time of the prepared epoxy resin matrix is shorter, but the viscosity is lower, so that the requirement of an extrusion process cannot be met. When the o-cresol novolac epoxy resin with the epoxy equivalent of 200-240 g/mol and the alicyclic epoxy resin with the epoxy equivalent of 180-220 g/mol are added into the system, the problems can be effectively solved, and the high temperature resistance of the system is also improved, probably because the bisphenol A epoxy resin has small epoxy equivalent, short molecular chain and easy movement, the curing process is accelerated, and the curing time is short; when the added o-cresol type novolac epoxy resin and the alicyclic epoxy resin are cured, the added o-cresol type novolac epoxy resin and the alicyclic epoxy resin are cooperated with bisphenol A type epoxy resin to form a three-dimensional structure with high crosslinking density, and the added o-cresol type novolac epoxy resin is rich in a phenolic aldehyde skeleton, so that excellent high-temperature resistance is shown. However, in a high-humidity and high-pressure environment, the hydrolysis and aging resistance of the matrix is reduced, which may be that more groups with high polarity, such as hydroxyl groups, ether groups and the like, are introduced, so that water is easily absorbed, and the hydrolysis and aging resistance of the matrix is reduced.
<Glycidyl amine epoxy resins>
The glycidyl amine epoxy resin is diaminodiphenylmethane tetraglycidyl amine epoxy resin and/or diglycidyl p-aminophenol TUY.AP epoxy resin.
In a preferred embodiment, the glycidyl amine epoxy resin is selected from the group consisting of diaminodiphenylmethane tetraglycidyl amine epoxy resins available from Hubei Xinrund chemical Co., Ltd.
<Curing agent>
The curing agent is selected from one or a combination of more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride and methyl nadic anhydride.
In a preferred embodiment, the curing agent comprises methyl tetrahydrophthalic anhydride and methyl nadic anhydride.
In a more preferred embodiment, the mass ratio of the methyltetrahydrophthalic anhydride to the methylnadic anhydride is (1.5-4): 1; more preferably, the mass ratio of the methyltetrahydrophthalic anhydride to the methylnadic anhydride is 2.5: 1.
<toughening agent>
The toughening agent is selected from one or a combination of more of carboxyl-terminated block copolymer, carboxyl-terminated butadiene-acrylonitrile rubber, fatty glycidyl ether, 1, 2-epoxy-3-phenoxypropane, organic silicon, polyester polyol and polycaprolactone polyol.
In a preferred embodiment, the toughening agent comprises a fatty glycidyl ether, 1, 2-epoxy-3-phenoxypropane, and a silicone.
In a more preferred embodiment, the mass ratio of the fatty glycidyl ether, the 1, 2-epoxy-3-phenoxypropane and the silicone is (0.3-0.5): (0.4-0.6): 1; more preferably, the mass ratio of the fatty glycidyl ether, the 1, 2-epoxy-3-phenoxypropane and the organosilicon is 0.4: 0.5: 1.
in a more preferred embodiment, the silicone is selected from the group consisting of 3- ((2,3) -glycidoxy) propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 5, 6-epoxyhexyltriethoxysilane, (3- (2, 3-epoxypropoxy) propyl) (2-methoxyethoxy) dimethylsilane, 2- (3, 4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane.
In a more preferred embodiment, the silicone is 3- ((2,3) -glycidoxy) propylmethyldimethoxysilane (CAS: 65799-47-5).
The addition of the fatty glycidyl ether can alleviate the occurrence of brittle fracture defect, but the curing time of the system is prolonged and the high-temperature resistance is reduced easily, especially when the addition of the fatty glycidyl ether is excessive. When 1, 2-epoxy-3-phenoxypropane and an organic silicon polymer are added into the system, and the mass ratio of the fatty glycidyl ether, the 1, 2-epoxy-3-phenoxypropane and the organic silicon polymer is controlled to be (0.3-0.5): (0.4-0.6): 1, particularly when 3- ((2,3) -glycidoxy) propyl methyl dimethoxysilane organosilicon is selected, the toughness and the high-temperature resistance of the system can be greatly improved on the basis of not increasing the curing time. This is probably because the aliphatic glycidyl ether does not have cyclic structures such as benzene ring, alicyclic ring and heterocyclic ring, and when the aliphatic glycidyl ether is added too much, the curing speed is reduced, and the crosslinking density is reduced, thereby affecting the high temperature resistance of the system. The 1, 2-epoxy-3-phenoxypropane and the organic silicon polymer in the system can be cooperated with the fatty glycidyl ether to react with the curing agent, so that the crosslinking density of the system can be increased on the premise of not influencing the curing speed, and the high temperature resistance can be improved.
<Accelerator>
The accelerant is an imidazole accelerant.
In one embodiment, the imidazole-based accelerator is selected from the group consisting of 1-methylimidazole, 2-phenylimidazole, dimethylbenzylamine, 1 benzyl 2 methylimidazole, 2 ethyl 4 methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2 undecylimidazole, and 1 cyanoethyl 2 methylimidazole.
In a preferred embodiment, the accelerator is 1-methylimidazole.
<Catalyst and process for preparing same>
The catalyst of the invention comprises a metal catalyst and a quaternary ammonium salt catalyst.
In a preferred embodiment, the mass ratio of the metal catalyst to the quaternary ammonium salt catalyst is 1: (1.2-1.6); more preferably, the mass ratio of the metal catalyst to the quaternary ammonium salt catalyst is 1: 1.4.
in a more preferred embodiment, the quaternary ammonium salt catalyst is selected from one or a combination of tetrabutylammonium chloride, tetrabutylammonium bromide and benzyltrimethylammonium chloride.
In a more preferred embodiment, the quaternary ammonium salt catalyst is tetrabutylammonium chloride; the metal catalyst is Cr+3Catalyst, purchased from DTCS corporation, usa under the HYCATTM3000S brand.
The second aspect of the invention provides a preparation method of the high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod, which at least comprises the following steps: and uniformly mixing the component A and the component B to obtain the composition.
In a preferred embodiment, the method for preparing the high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod at least comprises the following steps:
(1) stirring the component A to react to prepare a first mixture;
(2) stirring the component B for reaction to prepare a second mixture;
(3) mixing the first mixture and the second mixture to obtain the product.
In a more preferred embodiment, the method for preparing the high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod at least comprises the following steps:
(1) heating the component A in a reaction kettle, stirring for reaction, and cooling after the reaction to obtain a first mixture;
(2) heating the component B in another reaction kettle, stirring for reaction, and cooling after the reaction to obtain a second mixture;
(3) mixing the first mixture and the second mixture to obtain the product.
In a more preferred embodiment, the method for preparing the high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod at least comprises the following steps:
(1) heating the component A in a reaction kettle to 50-70 ℃, stirring at the speed of 50-70 rpm for reaction for 1-2 hours, and cooling to 20-30 ℃ after reaction to obtain a first mixture;
(2) heating the curing agent, the accelerator, the flexibilizer and the quaternary ammonium salt catalyst of the component B in another reaction kettle to 80-120 ℃, stirring and reacting for 1-2 hours at the speed of 50-70 rpm, cooling to 40-60 ℃ after reaction, adding the metal catalyst, and continuously stirring and reacting for 1-2 hours to obtain a second mixture;
(3) mixing the first mixture and the second mixture according to a ratio of epoxy equivalent to anhydride equivalent of 1: (0.9-1.1) and mixing to obtain the product.
<Epoxy equivalent>
The epoxy equivalent in the present invention is the amount (g/mol) of a resin having one epoxy group, that is, the average molecular weight of the epoxy resin divided by the number of epoxy groups contained in each molecule. The specific test method is as follows:
taking 2mL (mass fraction) of concentrated hydrochloric acid and 100mL of acetone, uniformly mixing in a dry conical flask, and standing for later use. 0.10-0.20 g of resin is weighed and placed in a 250mL conical flask, 20mL of hydrochloric acid-acetone solution is added by a pipette, and the mixture is shaken up and then kept stand for 30 min. Then, 1-2 drops of methyl red indicator are dripped, 0.1-0.2 mol/L NaOH standard solution is dripped to the end point of bright yellow color, the volume (mL) of consumed NaOH is recorded, and meanwhile, two parallel blank experiments are carried out.
In the formula: m: epoxy resin mass, g; v0V respectively represents the volume of the blank solution and the NaOH solution consumed by the sample, mL; c: molar concentration of NaOH standard solution, mol/L.
<Acid anhydride equivalent>
The equivalent weight of the acid anhydride is the molecular weight divided by the number of acid anhydride groups.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
The embodiment 1 of the invention provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod, which comprises a component A and a component B as preparation raw materials; the component A comprises 50 parts of bisphenol A epoxy resin, 15 parts of phenolic novolac type Novolak epoxy resin, 10 parts of alicyclic epoxy resin and 30 parts of glycidylamine epoxy resin in parts by weight;
the component B comprises 50 parts of curing agent, 5 parts of flexibilizer, 1 part of accelerant and 1 part of catalyst;
the bisphenol A epoxy resin has an epoxy equivalent of 170-200 g/mol.
The bisphenol A epoxy resin is purchased from Shandong De source epoxy technology Co., Ltd, and has the model number of DY-128E.
The phenolic novolac type Novolak epoxy resin comprises diphenol novolac epoxy resin and o-cresol novolac epoxy resin; the epoxy equivalent of the o-cresol novolac epoxy resin is 200-240 g/mol, and the o-cresol novolac epoxy resin is purchased from Vast chemical Co., Ltd., American type EPIKOTE 678; the mass ratio of the biphenyl novolac epoxy resin to the o-cresol novolac epoxy resin is 1.5: 1.
the raw materials for preparing the diphenol aldehyde epoxy resin comprise biphenyl phenol aldehyde and epoxy chloropropane; the molar ratio of the biphenyl phenol formaldehyde to the epoxy chloropropane is 1: 7.
the raw materials for preparing the diphenolaldehyde comprise 4, 4' -dimethoxymethylbiphenyl and phenol; the molar ratio of the 4, 4' -dimethoxymethylbiphenyl to the phenol is 1: 4.
the preparation process of the diphenolaldehyde comprises the following steps: adding 4, 4' -dimethoxymethylbiphenyl and phenol into a 250mL four-mouth bottle, adding oxalic acid to adjust the pH value to 5, stirring and refluxing for 4 hours under the nitrogen atmosphere, then heating to 185 ℃, and removing the excessive phenol by reduced pressure stirring to obtain the compound.
The preparation process of the diphenol aldehyde epoxy resin comprises the following steps: 20g of biphenyl phenol formaldehyde, 40g of epichlorohydrin and 3g of quaternary ammonium salt are sequentially added into a 250mL four-mouth bottle provided with an electric stirrer, a thermometer, a reflux condenser tube and a dropping funnel, heated and stirred to 65 ℃, and kept warm for 30 min. Then, 3.90g of 50 wt% NaOH solution was slowly added dropwise, the reaction was carried out for 2 hours, and the organic phase was separated by washing with water and then subjected to reduced pressure removal of epichlorohydrin. The resulting product was dissolved in methyl isobutyl ketone, and 0.650g of a 20 wt% NaOH solution was added thereto, followed by purification at 85 ℃ for 2 hours. And after the reaction is finished, washing with water until the pH value of the methyl isobutyl ketone solution is 7, and removing the methyl isobutyl ketone and the water by rotary evaporation to obtain the product.
The epoxy equivalent of the alicyclic epoxy resin is 180-220 g/mol; the alicyclic epoxy resin is bis ((3, 4-epoxycyclohexyl) methyl) adipate alicyclic epoxy resin which is purchased from Jinmingda New materials Co., Ltd, and is RE 26.
The glycidyl amine epoxy resin is selected from diaminodiphenylmethane tetraglycidyl amine epoxy resins, available from Hubei Xin run chemical Co., Ltd.
The curing agent comprises methyl tetrahydrophthalic anhydride and methyl nadic anhydride; the mass ratio of the methyltetrahydrophthalic anhydride to the methylnadic anhydride is 1.5: 1.
the toughening agent comprises fatty glycidyl ether, 1, 2-epoxy-3-phenoxypropane and organic silicon. The mass ratio of the fatty glycidyl ether, the 1, 2-epoxy-3-phenoxypropane and the organic silicon is 0.3: 0.4: 1.
the organic silicon is 3- ((2,3) -epoxypropoxy) propyl methyldimethoxysilane.
The accelerant is 1-methylimidazole.
The catalyst comprises a metal catalyst and a quaternary ammonium salt catalyst; the mass ratio of the metal catalyst to the quaternary ammonium salt catalyst is 1: 1.2; the metal catalyst is Cr+3Catalyst, purchased from DTCS corporation, usa under the designation HYCATTM 3000S; the quaternary ammonium salt catalyst is tetrabutyl ammonium chloride.
The preparation method of the high-temperature-resistant hydrolysis-resistant epoxy resin matrix for the sucker rod comprises the following steps:
(1) heating the component A to 60 ℃ in a reaction kettle, stirring and reacting for 1h at the speed of 60rpm, and cooling to 25 ℃ after reaction to obtain a first mixture;
(2) heating the curing agent, the accelerator, the flexibilizer and the quaternary ammonium salt catalyst of the component B in another reaction kettle to 100 ℃, stirring and reacting for 1h at the speed of 60rpm, cooling to 50 ℃ after reaction, adding the metal catalyst, and continuously stirring and reacting for 1h to obtain a second mixture;
(3) mixing the first mixture and the second mixture according to a ratio of epoxy equivalent to anhydride equivalent of 1: 1, mixing to obtain the product.
Example 2
The embodiment 2 of the invention provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod, which comprises a component A and a component B as preparation raw materials; the component A comprises 70 parts of bisphenol A epoxy resin, 25 parts of phenolic novolac type Novolak epoxy resin, 25 parts of alicyclic epoxy resin and 70 parts of glycidylamine epoxy resin in parts by weight;
the component B comprises 100 parts of curing agent, 20 parts of flexibilizer, 5 parts of accelerant and 5 parts of catalyst;
the bisphenol A epoxy resin has an epoxy equivalent of 170-200 g/mol.
The bisphenol A epoxy resin is purchased from Shandong De source epoxy technology Co., Ltd, and has the model number of DY-128E.
The phenolic novolac type Novolak epoxy resin comprises diphenol novolac epoxy resin and o-cresol novolac epoxy resin; the epoxy equivalent of the o-cresol novolac epoxy resin is 200-240 g/mol, and the o-cresol novolac epoxy resin is purchased from Vast chemical Co., Ltd., American type EPIKOTE 678; the mass ratio of the biphenyl novolac epoxy resin to the o-cresol novolac epoxy resin is 2: 1.
the raw materials for preparing the diphenol aldehyde epoxy resin comprise biphenyl phenol aldehyde and epoxy chloropropane; the molar ratio of the biphenyl phenol formaldehyde to the epoxy chloropropane is 1: 9.
the raw materials for preparing the diphenolaldehyde comprise 4, 4' -dimethoxymethylbiphenyl and phenol; the molar ratio of the 4, 4' -dimethoxymethylbiphenyl to the phenol is 1: 6.
the process for the preparation of the diphenolaldehyde is as in example 1.
The process for the preparation of said diphenolaldehyde epoxy resin is the same as in example 1.
The epoxy equivalent of the alicyclic epoxy resin is 180-220 g/mol; the alicyclic epoxy resin is bis ((3, 4-epoxycyclohexyl) methyl) adipate alicyclic epoxy resin which is purchased from Jinmingda New materials Co., Ltd, and is RE 26.
The glycidyl amine epoxy resin is selected from diaminodiphenylmethane tetraglycidyl amine epoxy resins, available from Hubei Xin run chemical Co., Ltd.
The curing agent comprises methyl tetrahydrophthalic anhydride and methyl nadic anhydride; the mass ratio of the methyl tetrahydrophthalic anhydride to the methyl nadic anhydride is 4: 1.
the toughening agent comprises fatty glycidyl ether, 1, 2-epoxy-3-phenoxypropane and organic silicon. The mass ratio of the fatty glycidyl ether, the 1, 2-epoxy-3-phenoxypropane and the organic silicon is 0.5: 0.6: 1.
the organic silicon is 3- ((2,3) -epoxypropoxy) propyl methyldimethoxysilane.
The accelerant is 1-methylimidazole.
The catalyst comprises a metal catalyst and a quaternary ammonium salt catalyst; the mass ratio of the metal catalyst to the quaternary ammonium salt catalyst is 1: 1.6; the metal catalyst is Cr+3Catalyst, purchased from DTCS corporation, usa under the designation HYCATTM 3000S; the quaternary ammonium salt catalyst is tetrabutyl ammonium chloride.
The preparation steps of the high temperature resistant hydrolysis resistant epoxy resin matrix for the sucker rod are the same as those of the embodiment 1.
Example 3
The embodiment 3 of the invention provides a high-temperature-resistant hydrolysis-resistant epoxy resin matrix for a sucker rod, which comprises a component A and a component B as preparation raw materials; the component A comprises 60 parts of bisphenol A epoxy resin, 20 parts of phenolic novolac Novolak epoxy resin, 17 parts of alicyclic epoxy resin and 50 parts of glycidylamine epoxy resin in parts by weight;
the component B comprises 75 parts of curing agent, 12 parts of flexibilizer, 3 parts of accelerant and 3 parts of catalyst;
the epoxy equivalent of the bisphenol A epoxy resin is 170-190 g/mol.
The bisphenol A epoxy resin is purchased from Shandong De source epoxy technology Co., Ltd, and has the model number of DY-128E.
The phenolic novolac type Novolak epoxy resin comprises diphenol novolac epoxy resin and o-cresol novolac epoxy resin; the epoxy equivalent of the o-cresol novolac epoxy resin is 200-240 g/mol, and the o-cresol novolac epoxy resin is purchased from Vast chemical Co., Ltd., American type EPIKOTE 678; the mass ratio of the biphenyl novolac epoxy resin to the o-cresol novolac epoxy resin is 1.7: 1.
the raw materials for preparing the diphenol aldehyde epoxy resin comprise biphenyl phenol aldehyde and epoxy chloropropane; the molar ratio of the biphenyl phenol formaldehyde to the epoxy chloropropane is 1: 8.
the raw materials for preparing the diphenolaldehyde comprise 4, 4' -dimethoxymethylbiphenyl and phenol; the molar ratio of the 4, 4' -dimethoxymethylbiphenyl to the phenol is 1: 5.
the process for the preparation of the diphenolaldehyde is as in example 1.
The process for the preparation of said diphenolaldehyde epoxy resin is the same as in example 1.
The epoxy equivalent of the alicyclic epoxy resin is 180-220 g/mol; the alicyclic epoxy resin is bis ((3, 4-epoxycyclohexyl) methyl) adipate alicyclic epoxy resin which is purchased from Jinmingda New materials Co., Ltd, and is RE 26.
The glycidyl amine epoxy resin is selected from diaminodiphenylmethane tetraglycidyl amine epoxy resins, available from Hubei Xin run chemical Co., Ltd.
The curing agent comprises methyl tetrahydrophthalic anhydride and methyl nadic anhydride; the mass ratio of the methyltetrahydrophthalic anhydride to the methylnadic anhydride is 2.5: 1.
the toughening agent comprises fatty glycidyl ether, 1, 2-epoxy-3-phenoxypropane and organic silicon. The mass ratio of the fatty glycidyl ether, the 1, 2-epoxy-3-phenoxypropane and the organic silicon is 0.4: 0.5: 1.
the organic silicon is 3- ((2,3) -epoxypropoxy) propyl methyldimethoxysilane.
The accelerant is 1-methylimidazole.
The catalyst comprises a metal catalyst and a quaternary ammonium salt catalyst; the mass ratio of the metal catalyst to the quaternary ammonium salt catalyst is 1: 1.4; the metal catalyst is Cr+3Catalyst, purchased from DTCS corporation, usa under the designation HYCATTM 3000S; the quaternary ammonium salt catalyst is tetrabutyl ammonium chloride.
The preparation steps of the high temperature resistant hydrolysis resistant epoxy resin matrix for the sucker rod are the same as those of the embodiment 1.
Comparative example 1
The embodiment of the invention is the same as that of the embodiment 3 in the comparison example 1, except that the bisphenol A type epoxy resin has an epoxy equivalent of 470-550 g/mol, is purchased from Dow chemical company of America and has a model number of DER 671.
Comparative example 2
The embodiment of the invention is the same as that of the embodiment 3, except that the epoxy equivalent of the alicyclic epoxy resin is 120-140 g/mol, and the alicyclic epoxy resin is 3, 4-epoxy cyclohexyl methyl 3, 4-epoxy cyclohexyl formate which is purchased from Guangzhou Viruna chemical company Limited and has the model of TaiLuck-2021X.
Comparative example 3
The invention provides a comparative example 3 of a high temperature resistant hydrolysis resistant epoxy resin matrix for a sucker rod, which is the same as the embodiment 3 in the specific implementation manner, and is characterized in that the epoxy equivalent of the o-cresol novolac epoxy resin is 190-210 g/mol, and the o-cresol novolac epoxy resin is purchased from Changchun artificial resin factory, Inc., and has the model number of CNE 202.
Comparative example 4
The comparative example 4 of the invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for sucker rod, the specific implementation is the same as example 3, except that no alicyclic epoxy resin.
Comparative example 5
The comparative example 5 of the invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for a sucker rod, the specific implementation manner is the same as that of example 3, except that the mass ratio of the diphenolaldehyde epoxy resin to the o-cresol type phenol aldehyde epoxy resin is replaced by 1.7: 2.
comparative example 6
The comparative example 6 of the invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for sucker rod, the specific implementation manner is the same as that of example 3, except that o-cresol novolac epoxy resin is not used.
Comparative example 7
Comparative example 7 of the present invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for sucker rod, the specific embodiment is the same as example 3, except that there is no biphenol aldehyde epoxy resin.
Comparative example 8
The comparative example 8 of the invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for sucker rod, the specific implementation manner is the same as that of example 3, except that no alicyclic epoxy resin or o-cresol novolac epoxy resin is used.
Comparative example 9
Comparative example 9 of the present invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for a sucker rod, the specific embodiment of which is the same as example 3, except that the mass ratio of the fatty glycidyl ether, 1, 2-epoxy-3-phenoxypropane and the silicone is replaced by 1: 0.5: 1.
comparative example 10
The comparative example 10 of the invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for sucker rod, and the specific implementation manner is the same as that of example 3, except that 1, 2-epoxy-3-phenoxypropane is not used.
Comparative example 11
Comparative example 11 of the present invention provides a high temperature and hydrolysis resistant epoxy resin matrix for sucker rods, which is prepared in the same manner as example 3 except that 3- ((2,3) -glycidoxy) propylmethyldimethoxysilane is replaced with butyltrimethoxysilane (CAS: 1067-57-8).
Comparative example 12
Comparative example 12 of the present invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for sucker rod, the specific embodiment is the same as example 3, except that there is no aliphatic glycidyl ether.
Comparative example 13
Comparative example 13 of the present invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for sucker rod, the specific embodiment is the same as example 3, except that no silicone.
Comparative example 14
The comparative example 14 of the invention provides a high temperature resistant hydrolysis resistant epoxy resin matrix for sucker rod, the specific implementation manner is the same as that of example 3, except that no toughening agent is used.
Performance testing
1. Viscosity measurement
The viscosities of the samples prepared in examples 1 to 3, comparative examples 1 to 4, comparative example 6 and comparative examples 8 to 9 were measured at 25 ℃ with a CAP2000 type viscometer, 10 parallel samples were set for each example, and the average value was recorded in mPas.
2. Gel time test
Firstly, heating a heating table with a temperature control device to 140 ℃, and then respectively taking 1g of samples prepared in examples 1-3, comparative example 1 and comparative example 9 and uniformly spreading the samples in a self-made mold after the temperature of the heating table is stable, and simultaneously recording the time. When the system is in a gel state and loses fluidity, stopping timing, wherein the time is the gelation time of the mixed system, setting 10 parallel samples for each example, and recording the average value in s.
3. Aging test for pressure resistance, hydrolysis resistance
The samples prepared in examples 1 to 3, comparative example 5 and comparative example 7 were cured and heated at 60 ℃ for 2 hours, and the mass was measured. Then placing the sample under the hydrothermal condition of 120 ℃ and 20MPa for 1 month, heating the sample at 60 ℃ for 2 hours, weighing the sample, performing mass test by adopting an electronic balance with the precision of 0.1mg, setting 10 parallel samples for each example, and recording the average value. The mass change rate is calculated as follows:
in the formula: m-mass change/%; w-mass after aging/g; w0-mass before aging/g.
4. Thermal performance testing
The glass transition temperature (Tg) of the epoxy matrix is used to characterize the thermal properties. After the samples prepared in examples 1 to 3 and comparative examples 1 to 14 were cured, the temperature was measured by a Mettler-Toledo DSC 821 ℃ type differential scanning calorimeter, the temperature rise rate was 10 ℃/min, the range was 20 to 300 ℃, and the flow rate was 200mL/min N2And (5) testing under protection.
5. Brittle fracture test
After the samples prepared in examples 1-3, comparative example 5, comparative example 7 and comparative examples 10-14 were cured, whether cracking or breaking occurred in the test samples was observed. Each example was set with 100 parallel samples, and the cracking and breakage probabilities, i.e. the number of cracked and broken samples, were recorded as a percentage of the total number tested.
TABLE 1
TABLE 2
| Viscosity (mPa. s) | Gel time(s) | Tg(℃) | |
| Comparative example 1 | 1000 | 120 | 159 |
| Comparative example 9 | 400 | 125 | 148 |
TABLE 3
| Viscosity (mPa. s) | Tg(℃) | |
| Comparative example 2 | 870 | 161 |
| Comparative example 3 | 900 | 164 |
| Comparative example 4 | 950 | 168 |
| Comparative example 6 | 520 | 146 |
| Comparative example 8 | 400 | 120 |
TABLE 4
TABLE 5
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The high-temperature-resistant hydrolysis-resistant epoxy resin matrix for the sucker rod is characterized in that the preparation raw materials comprise a component A and a component B; the component A comprises bisphenol A epoxy resin, phenolic novolac Novolak epoxy resin, alicyclic epoxy resin and glycidyl amine epoxy resin;
the component B comprises a curing agent, a toughening agent, an accelerant and a catalyst;
the bisphenol A epoxy resin has an epoxy equivalent of 130 to 300 g/mol.
2. The high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod as claimed in claim 1, wherein the component A comprises 40-80 parts by weight of bisphenol A epoxy resin, 10-30 parts by weight of novolac Novolac epoxy resin, 5-30 parts by weight of alicyclic epoxy resin, and 0-100 parts by weight of glycidylamine epoxy resin;
the component B comprises 30-120 parts of curing agent, 1-30 parts of toughening agent, 0-10 parts of accelerant and 0-10 parts of catalyst.
3. The high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod as claimed in claim 2, wherein the component A comprises 50 to 70 parts by weight of bisphenol A epoxy resin, 15 to 25 parts by weight of novolac Novolac epoxy resin, 10 to 25 parts by weight of alicyclic epoxy resin and 30 to 70 parts by weight of glycidylamine epoxy resin;
the component B comprises 50-100 parts of curing agent, 5-20 parts of toughening agent, 1-5 parts of accelerant and 1-5 parts of catalyst.
4. The high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod as claimed in claim 1, wherein the bisphenol A epoxy resin has an epoxy equivalent of 170 to 200 g/mol.
5. The high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod as claimed in any one of claims 1 to 4, wherein the novolac type Novolak epoxy resin is selected from one or more of phenol type novolac epoxy resin, o-cresol type novolac epoxy resin and biphenol aldehyde epoxy resin.
6. The high temperature and hydrolysis resistant epoxy resin matrix for the sucker rod as claimed in claim 1, wherein the accelerator is an imidazole accelerator.
7. The epoxy resin matrix of claim 6, wherein the imidazole accelerators are selected from the group consisting of 1-methylimidazole, 2-phenylimidazole, dimethylbenzylamine, 1 benzyl 2 methylimidazole, 2 ethyl 4 methylimidazole, 1 cyanoethyl 2 phenylimidazole, 2 undecylimidazole, and 1 cyanoethyl 2 methylimidazole.
8. The epoxy resin matrix of claim 1, wherein the curing agent is selected from one or more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, and methyl nadic anhydride.
9. The epoxy resin matrix of claim 1, wherein the catalyst comprises a metal catalyst and a quaternary ammonium salt catalyst.
10. The preparation method of the high-temperature-resistant hydrolysis-resistant epoxy resin matrix for the sucker rod according to any one of claims 1 to 9 is characterized by at least comprising the following steps: and uniformly mixing the component A and the component B to obtain the composition.
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| CN115124960A (en) * | 2022-07-21 | 2022-09-30 | 惠州广瑞合新材料科技有限公司 | High-temperature-resistant boiling-resistant epoxy resin pouring sealant and preparation method thereof |
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| CN104497271A (en) * | 2014-12-24 | 2015-04-08 | 济南圣泉集团股份有限公司 | Modified epoxy resin and modified epoxy resin composition |
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| US20140171551A1 (en) * | 2011-06-24 | 2014-06-19 | Air Products And Chemicals Inc. | Epoxy Resin Compositions Using Solvated Solids |
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| CN115124960A (en) * | 2022-07-21 | 2022-09-30 | 惠州广瑞合新材料科技有限公司 | High-temperature-resistant boiling-resistant epoxy resin pouring sealant and preparation method thereof |
| CN115124960B (en) * | 2022-07-21 | 2024-03-08 | 惠州广瑞合新材料科技有限公司 | High-temperature-resistant boiling-resistant epoxy resin pouring sealant and preparation method thereof |
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