CN101798380A - Method for preparing high-strength high-toughness epoxy resin system - Google Patents
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Abstract
The invention provides a method for preparing a high-strength high-toughness epoxy resin system, relates to a method for preparing the epoxy resin system, and solves the problems that the conventional epoxy resin system cannot simultaneously realize small viscosity and long working life of an epoxy resin liquid system before curing, and good mechanical performance of the epoxy resin after curing. The preparation method comprises the following steps: mixing and heating MBOEA and 660 to prepare modified curing agent; adding the modified curing agent into mixture of TDE-85 and E-51 for blending so as to prepare the epoxy resin liquid system; and curing the epoxy resin liquid system. The viscosity of the epoxy resin liquid system is between 700 and 1,000mPa.s, and the working life of the system is between 8 and 16 hours, thus meeting the requirement of composite material wet molding; in the cured epoxy resin, the tensile strength is between 80 and 100MPa, the tensile modulus is between 3.0 and 3.8GPa, and the elongation at break is between 4.0 and 7.0 percent. The method has simple process, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy-resin systems.
Background technology
Aspect pressurized vessel and pressure pipeline usefulness composite study, the research of strongthener has been experienced from the evolution of glass fibre to organic fibre and carbon fiber, and the application of novel enhanced material is greatly improved the performance of pressurized vessel and pressure pipeline; Yet in the research of resin particularly a little less than the research relatively aspect the toughening modifying of resin matrix, in order to guarantee the development demand of large-scale composite material pressurized vessel and pressure pipeline, further improve its over-all properties, in the development of new strongthener, the new type resin matrix that research has high-intensity high-tenacity and long pot life simultaneously becomes an important techniques approach.
The resin matrix that composite pressure vessel and pressure pipeline are commonly used is a Resins, epoxy, though the epoxy resin-base processing performance of utilizing anhydride curing agent curing to obtain is fine, cured article fragility is big, and shock resistance is relatively poor; Though adopt arylamine solidified agent solidified epoxy resin-base cured article fragility to make moderate progress, but it is (big such as viscosity that processing performance can not satisfy requirement of actual application, gel time is short etc.), lack the working life that is to say epoxy/amine resins matrix (gel time was less than 2 hours under 30 ℃ of temperature), when making the large-scale composite material goods so and needing molding time longer (5-12 hour), common epoxy/amine resins matrix just can't satisfy the moulding process requirement.The matrix used strength and toughness of high performance composite goods also is the scope of the performance of overriding concern simultaneously.
Summary of the invention
The objective of the invention is for solve that epoxy resin liquid system viscosity before existing epoxy-resin systems can not be realized solidifying simultaneously is little, working life long and solidify after the good problem of mechanical property of Resins, epoxy.The invention provides a kind of preparation method of high-strength high-toughness epoxy resin system.
The preparation method of high-strength high-toughness epoxy resin system of the present invention realizes by following steps: one, by weight with 40～45 part 3,3 ＇-diethyl 4,4 ＇-diamino methane (MBOEA) and 10～15 parts of epoxy propane butyl ethers (660) mix, and stir to be placed on to be incubated the modified firming agent that obtained liquid state in 1～3 hour under 70～80 ℃ of temperature; Two, by weight with 50～60 part 4,5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester (TDE-85) and 40～50 parts of bisphenol A diglycidyl ethers (E-51) mixing and stirring under 40～60 ℃ of temperature obtains composite epoxy resin; Three, the composite epoxy resin that obtains of the modified firming agent that 50～60 parts of step 1 are obtained and 90～110 parts of step 2 mixes, stir the epoxy resin liquid system; Four, the epoxy resin liquid system that step 3 is obtained is incubated 2～3h under 70～80 ℃ of temperature, be incubated 1.5～2.5h then under 110～125 ℃ of temperature, is incubated 4～6h again under 145～160 ℃ of temperature and obtains solidified Resins, epoxy; Every part conformance to standard of step 1 weight part to the step 3 wherein.
The preparation method of high-strength high-toughness epoxy resin system of the present invention selects 4 for use, 5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester (TDE-85) and 40～50 parts of bisphenol A diglycidyl ethers (E-51) are hybrid epoxy resin system, have reduced the production cost of only using TDE-85.Select 3 for use, 3 ＇-diethyl 4,4 ＇-diamino methane (MBOEA) is solidifying agent, epoxy propane butyl ether (660) is cured modified dose, after being incubated 1～3 hour under 70～80 ℃ of temperature, obtain the MBOEA solidifying agent after 660 modifications, uncle's hydrogen generation crosslinking reaction on oxirane ring in 660 molecules and the MBOEA molecule realizes the toughness reinforcing graft modification of MBOEA and the transformation of solid state powder to low-viscosity (mobile) liquid is arranged.Wherein, the effect of epoxy propane butyl ether (660) has three: the toughness that one, increases solidifying agent by the adding of linear structure; Two, destroy the crystalline network of Powdered 3,3 ＇-diethyl 4,4 ＇-diamino methane (MBOEA) solidifying agent, make its not recrystallize, realize the favorable manufacturability energy; Three, increase the viscosity of epoxy resin-base effectively, guarantee intensity and modulus that it is good simultaneously.
The curing of epoxy-resin systems of the present invention (step 4) adopts the sectional type heating heat preserving method, be divided into three holding stages,---being incubated 1.5～2.5h under 110～125 ℃ of temperature---is incubated 4～6h under 145～160 ℃ of temperature to be incubated 2～3h under 70～80 ℃ of temperature, temperature, soaking time is a key parameter of the present invention, the present invention adopts above-mentioned heat tracing curing, the tensile strength of the cured article that obtains (Resins, epoxy) reaches 80～100MPa, flexural strength reaches 160～200MPa, tension set is 4.0～7.0%, compressive strength reaches 120～150MPa, tensile modulus is 3～5GPa, modulus in flexure is 3～5GPa, and modulus of compression is 3～5GPa, and heat-drawn wire is 120～135 ℃, degree of cure reaches 98%, and density is 1.28g/m
3The processing performance of this epoxy resin cured product has reached the requirement to epoxy resin-base of composite pressure vessel and pressure pipeline fully, and this epoxy resin-base and carbon fiber can effectively overcome the big shortcoming of carbon fiber fragility with the finished product of the Wrapping formed preparation of large-scale housing wet method, is with a wide range of applications.
The present invention through epoxy resin liquid system that step 3 obtains under 30 ℃ of temperature, gelatin viscosity is 700～1000mPas, and epoxy resin liquid system gelatin viscosity does not change after placing 10h, reach 8～16h the working life that is epoxy resin liquid system glue, can satisfy the Wrapping formed processing requirement to epoxy-resin systems of matrix material wet method fully.The apparent activation energy of the epoxy resin liquid system that obtains through step 3 is 56.23KJ/mol, and reaction order is 0.92; Reaction rate constant K in the time of 25 ℃
25=9.92 * 10
-8Min
-1, the reaction rate constant K in the time of 100 ℃
100=9.51 * 10
-5Min
-1The apparent activation energy of epoxy resin liquid system is higher, and at the low temperature low activity, the high temperature high reactivity is given epoxy resin adhesive liquid long pot life at low temperatures.The epoxy-resin systems of gained has good comprehensive performances after step 4 is solidified again.
Preparation method of the present invention is simple, operates simple and easy, scientific strong and be applicable to suitability for industrialized production.When the epoxy resin liquid system before having realized solidifying had the advantage of the good performance of technical process that viscosity is little, working life is long, the mechanical property of the Resins, epoxy that obtains after the curing was also fine.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment high-strength high-toughness epoxy resin system realizes by following steps: one, by weight with 40～45 part 3,3 ＇-diethyl 4,4 ＇-diamino methane (MBOEA) and 10～15 parts of epoxy propane butyl ethers (660) mix, and stir to be placed on to be incubated the modified firming agent that obtained liquid state in 1～3 hour under 70～80 ℃ of temperature; Two, by weight with 50～60 part 4,5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester (TDE-85) and 40～50 parts of bisphenol A diglycidyl ethers (E-51) mixing and stirring under 40～60 ℃ of temperature obtains composite epoxy resin; Three, the composite epoxy resin that obtains of the modified firming agent that 50～60 parts of step 1 are obtained and 90～110 parts of step 2 mixes, stir the epoxy resin liquid system; Four, the epoxy resin liquid system that step 3 is obtained is incubated 2～3h under 70～80 ℃ of temperature, be incubated 1.5～2.5h then under 110～125 ℃ of temperature, is incubated 4～6h again under 145～160 ℃ of temperature and obtains solidified Resins, epoxy; Every part conformance to standard of step 1 weight part to the step 3 wherein.
TDE-85 Resins, epoxy is a kind of Resins, epoxy with special performance in the present embodiment, have three epoxy group(ing) on its molecular structure, higher oxirane value (about 0.85) is arranged, and be a low viscous resin (about about 1500 centipoises of viscosity at ambient temperature), as a novel trifunctional Resins, epoxy, the reactive behavior of TDE-85 Resins, epoxy is bigger than general cycloaliphatic epoxy resin, and it is low to the aliphatic amide reactive behavior to have overcome cycloaliphatic epoxy resin, almost can not the solidified shortcoming to imidazoles and tertiary amine, characteristics on this molecular structure, give formulating of recipe person and can select more solidifying agent, thereby its range of application and value have been enlarged greatly, and same bisphenol A type epoxy resin, o-phthalic acid diglycidyl ester Resins, epoxy etc. is compared, the flexural strength of TDE-85 cured article and tensile strength height, good heat resistance, the cross-linking density of cured article is big.But owing to costing an arm and a leg of TDE-85, so we have selected performance also to mix use with it than more excellent bisphenolA-glycidol ether epoxy resin (E-51).Because the Wrapping formed viscosity of resin system that requires of wet method is lower, and make the lower acid anhydride type curing agent of resin viscosity the gypsum material core of container and pipeline is had aggressiveness, and take all factors into consideration other factors again, used resin formula adopts amine curing agent.Aliphatics amine solidifying agent alkalescence is high, reactive behavior height during as the resin system solidifying agent, the usage period that will reduce resin system significantly, be unfavorable for technological operation, therefore, we select for use in the aromatic amine toughness preferably MBOEA as solidifying agent.
The epoxy resin liquid system that the present embodiment step 3 obtains is under 30 ℃ of temperature, the epoxy-resin systems gelatin viscosity is 700～1000mPas, and the epoxy-resin systems gelatin viscosity does not change after placing 10h, be the usage period 8～16h of epoxy-resin systems glue, can satisfy the Wrapping formed processing requirement of matrix material wet method fully epoxy-resin systems.Sectional type heat tracing curing through step 4, the tensile strength of the Resins, epoxy finished product that obtains reaches 80～100MPa, flexural strength reaches 160～200MPa, and tension set is 4.0～7.0%, and compressive strength reaches 120～150MPa, tensile modulus is 3～5GPa, modulus in flexure is 3～5GPa, and modulus of compression is 3～5GPa, and heat-drawn wire is 120～135 ℃, degree of cure reaches 98%, and density is 1.28g/m
3The processing performance of the cured article of this epoxy-resin systems has reached the requirement to epoxy resin-base of composite pressure vessel and pressure pipeline fully, and this epoxy resin-base and carbon fiber can effectively overcome the big shortcoming of carbon fiber fragility with the finished product of the Wrapping formed preparation of large-scale housing wet method, is with a wide range of applications.
Embodiment two: what present embodiment and embodiment one were different is by weight 42～44 parts of 3,3 ＇-diethyl 4,4 ＇-diamino methane (MBOEA) and 12～14 parts of epoxy propane butyl ethers (660) to be mixed in the step 1.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is by weight 43 parts of 3,3 ＇-diethyl 4,4 ＇-diamino methane (MBOEA) and 13 parts of epoxy propane butyl ethers (660) to be mixed in the step 1.Other step and parameter are identical with embodiment one.
Embodiment four: present embodiment and embodiment one, two or three are different is to place in the step 1 to be incubated 1.5～2.5 hours under 72～78 ℃ of temperature and to obtain liquid modified firming agent.Other step and parameter are identical with embodiment one, two or three.
Embodiment five: present embodiment and embodiment one, two or three are different is to place in the step 1 that insulation obtained liquid modified firming agent in 2 hours under 75 ℃ of temperature.Other step and parameter are identical with embodiment one, two or three.
Embodiment six: what present embodiment was different with one of embodiment one to five is by weight with 52～58 part 4 in the step 2,5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester (TDE-85) and 42～46 parts of bisphenol A diglycidyl ethers (E-51) mixing and stirring under 40～60 ℃ of temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different with one of embodiment one to five is by weight with 56 part 4 in the step 2,5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester (TDE-85) and 45 parts of bisphenol A diglycidyl ethers (E-51) mixing and stirring under 40～60 ℃ of temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment eight: present embodiment is different with one of embodiment one to seven be in the step 2 under 46～55 ℃ of temperature mixing and stirring get composite epoxy resin.Other step and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different with one of embodiment one to seven be in the step 2 under 50 ℃ of temperature mixing and stirring get composite epoxy resin.Other step and parameter are identical with one of embodiment one to seven.
Embodiment ten: present embodiment is different with one of embodiment one to nine is that the epoxy resin liquid system that in the step 4 step 3 obtained places under 75 ℃ of temperature and is incubated 2.5h.Other step and parameter are identical with one of embodiment one to nine.
Embodiment 11: what present embodiment was different with one of embodiment one to ten is to be incubated 1.8～2.3h then under 115～120 ℃ of temperature in the step 4.Other step and parameter are identical with one of embodiment one to ten.
Embodiment 12: what present embodiment was different with one of embodiment one to ten is to be incubated 2h then under 118 ℃ of temperature in the step 4.Other step and parameter are identical with one of embodiment one to ten.
Embodiment 13: what present embodiment was different with one of embodiment one to 12 is to be incubated 4.5～5.5h again under 148～155 ℃ of temperature in the step 4.Other step and parameter are identical with one of embodiment one to 12.
Embodiment 14: what present embodiment was different with one of embodiment one to 12 is to be incubated 5h again under 150 ℃ of temperature in the step 4.Other step and parameter are identical with one of embodiment one to 12.
Embodiment 15: the preparation method of present embodiment high-strength high-toughness epoxy resin system realizes by following steps: one, by weight with 43 part 3,3 ＇-diethyl 4,4 ＇-diamino methane (MBOEA) and 13 parts of epoxy propane butyl ethers (660) mix, and stir to be placed on to be incubated the modified firming agent that obtained liquid state in 2 hours under 75 ℃ of temperature; Two, by weight with 56 part 4,5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester (TDE-85) and 45 parts of bisphenol A diglycidyl ethers (E-51) mixing and stirring under 50 ℃ of temperature gets composite epoxy resin; Three, the composite epoxy resin that obtains of the modified firming agent that 56 parts of step 1 are obtained and 101 parts of step 2 mixes, stir the epoxy resin liquid system; Four, the epoxy resin liquid system that step 3 is obtained is incubated 2.5h under 75 ℃ of temperature, be incubated 2h then under 118 ℃ of temperature, is incubated 5h again under 150 ℃ of temperature, the Resins, epoxy after must solidifying; Wherein step 1 weight part to the step 3 is 100g/ part.
Present embodiment through epoxy resin liquid system that step 3 obtains under 30 ℃ of temperature, the epoxy-resin systems gelatin viscosity is 700mPas, and the epoxy-resin systems gelatin viscosity does not change after placing 16h, be 16h the working life that is the epoxy-resin systems glue, can satisfy the Wrapping formed processing requirement to epoxy-resin systems of wet method fully.The apparent activation energy of the epoxy resin liquid system that present embodiment obtains is 56.23KJ/mol, and reaction order is 0.92.Reaction rate constant K in the time of 25 ℃
25=9.92 * 10
-8Min
-1, the reaction rate constant K in the time of 100 ℃
100=9.51 * 10
-5Min
-1The apparent activation energy of epoxy resin liquid system is higher, and at the low temperature low activity, the high temperature high reactivity is given epoxy resin adhesive liquid long pot life at low temperatures.
The finished product that after step 4 is solidified, obtains tensile strength reach 100MPa, flexural strength reaches 200MPa, tension set is 7.0%, compressive strength reaches 150MPa, and tensile modulus is 5GPa, and modulus in flexure is 5GPa, modulus of compression is 5GPa, heat-drawn wire is 135 ℃, and degree of cure reaches 98%, and density is 1.28g/m
3The processing performance of this epoxy-resin systems cured article has reached the requirement to epoxy resin-base of composite pressure vessel and pressure pipeline fully, and this epoxy resin-base and carbon fiber can effectively overcome the big shortcoming of carbon fiber fragility with the finished product of the Wrapping formed preparation of large-scale housing wet method, is with a wide range of applications.
Embodiment 16: the preparation method of present embodiment high-strength high-toughness epoxy resin system realizes by following steps: one, by weight with 45 part 3,3 ＇-diethyl 4,4 ＇-diamino methane (MBOEA) and 15 parts of epoxy propane butyl ethers (660) mix, and stir to be placed on to be incubated the modified firming agent that obtained liquid state in 1.5 hours under 80 ℃ of temperature; Two, by weight with 50 part 4,5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester (TDE-85) and 40 parts of bisphenol A diglycidyl ethers (E-51) mixing and stirring under 60 ℃ of temperature gets composite epoxy resin; Three, the composite epoxy resin that obtains of the modified firming agent that 60 parts of step 1 are obtained and 90 parts of step 2 mixes, stir the epoxy resin liquid system; Four, the epoxy resin liquid system that step 3 is obtained is incubated 2h under 70 ℃ of temperature, be incubated 2h then under 115 ℃ of temperature, is incubated 4h again under 145 ℃ of temperature, obtains finished product, i.e. epoxy-resin systems; Wherein step 1 weight part to the step 3 is 100g/ part.
Present embodiment through epoxy resin liquid system that step 3 obtains under 30 ℃ of temperature, the epoxy-resin systems gelatin viscosity is 800mPas, and the epoxy-resin systems gelatin viscosity does not change after placing 15h, be the usage period 15h of epoxy-resin systems glue, can satisfy the Wrapping formed processing requirement of wet method fully epoxy-resin systems.The apparent activation energy of the epoxy-resin systems that present embodiment obtains is 56.23KJ/mol, and reaction order is 0.92.Reaction rate constant K in the time of 25 ℃
25=9.92 * 10
-8Min
-1, the reaction rate constant K in the time of 100 ℃
100=9.51 * 10
-5Min
-1The apparent activation energy of epoxy-resin systems is higher, and at the low temperature low activity, the high temperature high reactivity is given epoxy resin adhesive liquid long pot life at low temperatures.Therefore the gained epoxy-resin systems has good comprehensive performances.
The tensile strength of the Resins, epoxy finished product that obtains through step 4 reaches 80MPa, flexural strength reaches 160MPa, tension set is 4.0%, compressive strength reaches 120MPa, and tensile modulus is 3GPa, and modulus in flexure is 3GPa, modulus of compression is 3GPa, heat-drawn wire is 120 ℃, and degree of cure reaches 98%, and density is 1.28g/m
3The processing performance of this epoxy-resin systems cured article has reached the requirement to epoxy resin-base of composite pressure vessel and pressure pipeline fully, and this epoxy resin-base and carbon fiber can effectively overcome the big shortcoming of carbon fiber fragility with the finished product of the Wrapping formed preparation of large-scale housing wet method, is with a wide range of applications.
Claims (10)
1. the preparation method of a high-strength high-toughness epoxy resin system, the preparation method who it is characterized in that high-strength high-toughness epoxy resin system realizes by following steps: one, by weight with 40～45 part 3,3 ＇-diethyl 4,4 ＇-diamino methane and 10～15 parts of epoxy propane butyl ethers mix, and stir to be placed on to be incubated the modified firming agent that obtained liquid state in 1～3 hour under 70～80 ℃ of temperature; Two, by weight with 50～60 part 4,5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester and 40～50 parts of bisphenol A diglycidyl ethers mixing and stirring under 40～60 ℃ of temperature obtain composite epoxy resin; Three, the composite epoxy resin that obtains of the modified firming agent that 50～60 parts of step 1 are obtained and 90～110 parts of step 2 mixes, stir the epoxy resin liquid system; Four, the epoxy resin liquid system that step 3 is obtained is incubated 2～3h under 70～80 ℃ of temperature, be incubated 1.5～2.5h then under 110～125 ℃ of temperature, is incubated 4～6h again under 145～160 ℃ of temperature and obtains solidified Resins, epoxy; Every part conformance to standard of step 1 weight part to the step 3 wherein.
2. the preparation method of high-strength high-toughness epoxy resin system according to claim 1 is characterized in that by weight 42～44 parts of 3,3 ＇-diethyl 4,4 ＇-diamino methane and 12～14 parts of epoxy propane butyl ethers being mixed in the step 1.
3. the preparation method of high-strength high-toughness epoxy resin system according to claim 1 is characterized in that by weight 43 parts of 3,3 ＇-diethyl 4,4 ＇-diamino methane and 13 parts of epoxy propane butyl ethers being mixed in the step 1.
4. according to the preparation method of claim 1,2 or 3 described high-strength high-toughness epoxy resin systems, it is characterized in that placing in the step 1 being incubated the modified firming agent that obtained liquid state in 1.5～2.5 hours under 72～78 ℃ of temperature.
5. the preparation method of high-strength high-toughness epoxy resin system according to claim 4, it is characterized in that in the step 2 by weight with 52～58 part 4,5-epoxy cyclohexane 1,2-dioctyl phthalate 2-glycidyl ester and 42～46 parts of bisphenol A diglycidyl ethers mixing and stirring under 40～60 ℃ of temperature.
6. according to the preparation method of claim 1,2,3 or 5 described high-strength high-toughness epoxy resin systems, it is characterized in that in the step 2 that mixing and stirring gets composite epoxy resin under 46～55 ℃ of temperature.
7. the preparation method of high-strength high-toughness epoxy resin system according to claim 6 is characterized in that the epoxy resin liquid system that in the step 4 step 3 is obtained is incubated 2.5h under 75 ℃ of temperature.
8. according to the preparation method of claim 1,2,3,5 or 7 described high-strength high-toughness epoxy resin systems, it is characterized in that under 115～120 ℃ of temperature, being incubated 1.8～2.3h then in the step 4.
9. the curing of long pot life epoxy-resin systems according to claim 8 is characterized in that being incubated 4.5～5.5h again under 148～155 ℃ of temperature in the step 4.
10. the curing of long pot life epoxy-resin systems according to claim 8 is characterized in that being incubated 5h again under 150 ℃ of temperature in the step 4.
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| CN105131255A (en) * | 2015-09-30 | 2015-12-09 | 西安超码复合材料有限公司 | High-temperature-resistant resin |
| CN105542395A (en) * | 2015-12-24 | 2016-05-04 | 中国电力科学研究院 | Toughened and reinforced epoxy resin composition |
| CN106634450A (en) * | 2016-09-12 | 2017-05-10 | 鞍钢集团矿业有限公司 | Ore pulp pipeline inner wall wear-resistant coating as well as preparation and coating method thereof |
| CN106634450B (en) * | 2016-09-12 | 2019-03-29 | 鞍钢集团矿业有限公司 | A kind of ore pulp pipeline inner wall wear-resistant paint and its preparation and spraying method |
| CN106479126A (en) * | 2016-09-27 | 2017-03-08 | 山东泰山瑞豹复合材料有限公司 | A kind of bicycle structure epoxy resin toughened system and preparation method thereof |
| CN107629192A (en) * | 2017-09-21 | 2018-01-26 | 上海稳优实业有限公司 | The preparation method of fire-retardant electrically epoxy-resin systems |
| CN111614189A (en) * | 2019-02-24 | 2020-09-01 | 毅力科技有限公司 | Driving device and assembling method thereof |
| CN111057218A (en) * | 2019-12-31 | 2020-04-24 | 达森(天津)材料科技有限公司 | Preparation method of special anti-corrosion high-temperature-resistant epoxy resin for oil extraction sucker rod |
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Open date: 20100811 |