CN102827457A - Epoxy resin composition for automobile compressed natural gas steel inner liner ring-direction winding gas cylinder, and preparation method thereof - Google Patents
Epoxy resin composition for automobile compressed natural gas steel inner liner ring-direction winding gas cylinder, and preparation method thereof Download PDFInfo
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Abstract
The invention provides an epoxy resin composition for an automobile compressed natural gas steel inner liner ring-direction winding gas cylinder, which comprises epoxy resin mixture, curing agent and curing accelerator by weight ratio of 100: 50-100: 0.1-5.0, wherein the epoxy resin mixture comprises epoxy resin, diluent and flexibilizer by weight ratio of 100: 5-30: 5-50; the flexibilizer is mixture of fatty alcohol glycidyl ether and polyurethane or nitrile rubber; and the weight ratio between the fatty alcohol glycidyl ether and the polyurethane or the nitrile rubber is 10: 1-5. The composite material prepared by soaking glass fiber into the epoxy resin composition has better mechanical property. Furthermore, the epoxy resin composition also has the characteristics of low viscosity, wettability on the glass fiber, good construction technology and the like. The invention also provides a preparation method of the epoxy resin composition for the automobile compressed natural gas steel inner liner ring-direction winding gas cylinder.
Description
Technical field
The present invention relates to the epoxy resin technical field, particularly a kind of composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder and preparation method thereof.
Background technology
As everyone knows, the compressed natural gas gas cylinder is the pressurized vessel in order to storing compressed natural gas (CNG).Wherein, the compressed natural gas used as vehicle fuel gas cylinder comprises metal inner tube hoop winding gas cylinder and the full winding gas cylinder of plastics inner bag (overall plastic matrix material gas cylinder) etc.Overall plastic matrix material CNG gas cylinder exists that three-dimensional winding process is complicated, bottleneck and non-metallic inner liner combine and resistance to air loss is relatively poor, to the material and the shaped design of metal bottleneck have relatively high expectations, low temperature lower liner and matrix material occurs peeling off or catabiosis, non-metallic inner liner resin system temperature tolerance are poor, water detonation pressure power and the defectives such as poor stability of fatigue lifetime.Than overall plastic matrix material CNG gas cylinder, the metal inner tube hoop twines the CNG gas cylinder and still on price, all has very remarkable advantages from moulding process.Therefore, wherein steel inner bag hoop twines the CNG gas cylinder and is widely used at home.
In compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder; The matrix used resin of winding layer matrix material is thermoset or thermoplastic resin; Like epoxy resin, modified epoxy, polyamide resin and vinyl resins etc.; It plays the effect that connects fiber, transmits stress as main matrix material.Wherein, The organic high molecular compound that contains two or more epoxide groups in the epoxy resin general reference molecule; Can form and insoluble, infusiblely have the cancellated superpolymer of three-dimensional through adding solidifying agent generation crosslinking reaction, thereby show excellent physical and mechanical performance and chemical property.Therefore, epoxy resin is widely used as the matrix resin of winding layer matrix material.Granted publication number discloses a kind of compressed natural gas bottle special material of epoxy resin for the Chinese patent document of CN1239608C.This compressed natural gas bottle special material of epoxy resin is made up of the thinner of 100 parts by weight of epoxy resin, 5 ~ 20 weight parts, the solidifying agent of 75 ~ 85 weight parts, the promotor of 0.4 ~ 4 weight part; Wherein, It is raw material that epoxy resin adopts dihydroxyphenyl propane, epoxy chloropropane; Through in the preparation process, strengthening the consumption of epoxy chloropropane, the mol ratio of control epoxy chloropropane/dihydroxyphenyl propane is more than 8, and product viscosity is 7000mPa.s ~ 11000mPa.s; Thinner adopts single, double epoxy compounds blend; The weight ratio of mono-epoxy compounds and diepoxides is 1:3 ~ 1:5; Mono-epoxy compounds is selected from the butanols glycidyl ether, diepoxides one or more the mixture in glycol glycidyl ether, DGEEG, the Ucar 35 glycidyl ether of selecting oneself; By weight 100:4, reaction 1 h ~ made solidifying agent in 3 hours under 80 ℃ ~ 100 ℃ temperature by methyl tetrahydro phthalic anhydride and Ucar 35; Promotor is selected from 2,4, a kind of in three-2-ethylhexoate of 6-three (methylamino-methyl) phenol, benzyldimethylamine, 2-(dimethylamino methyl) phenol.
Above-mentioned compressed natural gas special material of epoxy resin has that pot life is long at normal temperatures, viscosity is low, impregnability is good; Characteristics such as middle warm pot life down is short; But; Only about 1150MPa, interlaminar shear strength is about 73.3MPa to the tensile strength of the matrix material that makes with its impregnated glass fiber, and mechanical property remains further to be improved.
Summary of the invention
In order to solve above technical problem; The present invention provides a kind of composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder and preparation method thereof; Adopt the said composition epoxy resin impregnated glass fiber that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder to make matrix material, it has mechanical property preferably.
The present invention provides a kind of composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder, comprises epoxy resin composition, solidifying agent and curing catalyst that weight ratio is 100:50 ~ 100:0.1 ~ 5.0;
Said epoxy resin composition comprises epoxy resin, thinner and the toughner that weight ratio is 100:5 ~ 30:5 ~ 50;
Said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril, and the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 5.
Preferably, the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 3.
Preferably, said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether is that carbochain is 12 ~ 14 alkyl glycidyl ether.
Preferably, said paracril is nbr carboxyl terminal or hydroxy'terminated butadiene nitrile rubber.
Preferably, said epoxy resin composition comprises epoxy resin, thinner and the toughner that weight ratio is 100:10 ~ 20:10 ~ 30.
Preferably, said thinner is n-butyl glycidyl ether, phenyl glycidyl ether or benzyl glycidyl ether.
Preferably, comprise epoxy resin composition, solidifying agent and the curing catalyst that weight ratio is 100:75 ~ 80:0.5 ~ 3.0.
Preferably, said solidifying agent is methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride.
Preferably, said curing catalyst is three (dimethylamino methyl) phenol, benzyldimethylamine or trolamine.
The present invention provides a kind of preparation method who is used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder, may further comprise the steps:
With weight ratio is epoxy resin, thinner and the toughner mixing of 100:5 ~ 30:5 ~ 50; Obtain epoxy resin composition; Said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril, and the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 5;
With weight ratio is said epoxy resin composition, solidifying agent and the curing catalyst mixing of 100:50 ~ 100:0.1 ~ 5.0, obtains being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder.
Compared with prior art; The present invention is epoxy resin, thinner and the toughner mixing of 100:5 ~ 30:5 ~ 50 with weight ratio; Obtain epoxy resin composition; Said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril, and the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 5; With weight ratio is said epoxy resin composition, solidifying agent and the curing catalyst mixing of 100:50 ~ 100:0.1 ~ 5.0, obtains being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder.The present invention is a toughner with the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril; The main polymer chain molecule contains reactive group in the said toughner; Can react with the reactive group in the epoxy resin; Formation is that " island ", connection phase epoxy resin are " island structure " in " sea " with the main polymer chain disperse phase, thereby reaches toughness reinforcing purpose, shows as stretching, shearing resistance raising.Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether snappiness is good in the said toughner, and apolar surfaces is had wellability, can with urethane or paracril acting in conjunction, increase substantially stretching, the shearing resistance of the matrix material of follow-up formation.Experimental result shows; Adopt the composition epoxy resin impregnated glass fiber that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder provided by the invention; Form matrix material through solidifying to wait; Its tensile strength is more than 1333MPa, and interlaminar shear strength can reach 89.1MPa, promptly has mechanical property preferably.
In addition; The composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder provided by the invention has that viscosity is low, the usage period is long, curing speed is evenly adjustable, exothermic peak is low, to characteristics such as spun glass wellability and construction technology are good, be beneficial to application.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The invention provides a kind of composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder, comprise epoxy resin composition, solidifying agent and curing catalyst that weight ratio is 100:50 ~ 100:0.1 ~ 5.0;
Said epoxy resin composition comprises epoxy resin, thinner and the toughner that weight ratio is 100:5 ~ 30:5 ~ 50;
Said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril, and the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 5.
The resin system of winding layer matrix material has material impact to the aspects such as mechanical property, resistance toheat and aging resistance of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder, and this has following requirement to said resin system: fiber is had good wellability; The unit elongation that has bondd and had higher intensity and adapt after solidifying with fiber; Has lower initial viscosity; Have lower cure shrinkage and hypotoxicity etc.
The composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder provided by the invention is a main ingredient with epoxy resin, thinner, toughner, solidifying agent, curing catalyst; Wherein, said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril.Said composition epoxy resin modest viscosity, the usage period that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder is long, curing performance is excellent, and its cured article has mechanical property preferably, is beneficial to application.
In the present invention; The said composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder comprises epoxy resin composition, solidifying agent and the curing catalyst that weight ratio is 100:50 ~ 100:0.1 ~ 5.0, preferably comprises epoxy resin composition, solidifying agent and curing catalyst that weight ratio is 100:75 ~ 80:0.5 ~ 3.0.
In the present invention, said epoxy resin composition comprises epoxy resin, thinner and the toughner that weight ratio is 100:5 ~ 30:5 ~ 50, preferably comprises epoxy resin, thinner and toughner that weight ratio is 100:10 ~ 20:10 ~ 30.
Wherein, said epoxy bond power is strong and the curing post-shrinkage ratio is little, is used for the resin system of gas cylinder winding layer matrix material more.The present invention does not have particular restriction to said epoxy resin; Said epoxy resin is preferably one or more of bisphenol A type epoxy resin, bisphenol f type epoxy resin and polyfunctional epoxy resin; Bisphenol A type epoxy resin more preferably, it has following characteristics: high purity, high epoxy value, LV; Can form multiple performance excellent in curing thing with multiple solidifying agent, catalyzer and additive, almost can satisfy various request for utilizations; Good manufacturability does not produce the small molecules volatile matter basically during curing; Can be dissolved in multiple solvent; Cured article has very high intensity and cohesive strength; Have certain thermoset, toughness and thermotolerance etc., that is, it has excellent comprehensive performances, and cost is low.Said bisphenol A type epoxy resin such as CYD-128 epoxy resin, epoxy resin E-51 etc.; Said polyfunctional epoxy resin such as TDE-85 etc.
Said thinner can reduce the viscosity of epoxy resin and be convenient to processing, also can play the effect that cuts down finished cost.The present invention does not have particular restriction to said thinner, and said thinner is preferably n-butyl glycidyl ether, phenyl glycidyl ether or benzyl glycidyl ether, and more preferably benzyl glycidyl ether is the product of XY692 like the trade mark.Said benzyl glycidyl ether is colourless transparent liquid, high epoxy value, has the active glycidyl ether of rigidity phenyl ring and monocycle oxygen groups that molecular formula is C
6H
5CH
2OCH
2(CHCH
2) O, its proportion 0.98, smell is little and almost do not have bad smell, toxicity is low, volatility is low, chemicalstability is good, not only is beneficial to the Working environment protection, and less to the product property influence.The consumption of said thinner is the 5wt% ~ 30wt% of said epoxy resin, is preferably 10wt% ~ 20wt%.
Said toughner can lower the fragility of resin system, increases toughness.In the present invention, said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril.Wherein, the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 5, is preferably 10:1 ~ 3.The consumption of said toughner is the 5wt% ~ 50wt% of said epoxy resin, is preferably 10wt% ~ 30wt%.
Said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether is a kind of glycidyl ether that has the Fatty Alcohol(C12-C14 and C12-C18) monocycle oxygen groups of long flexible chain structure, is preferably carbochain and is 12 ~ 14 alkyl glycidyl ether, is the product of XY748 like the trade mark.Said carbochain is that 12 ~ 14 alkyl glycidyl ether (AGE) is the transparent liquid of a kind of LV, low toxicity, low volatility, colorless and odorless, monofunctional, and molecular formula is C
12 ~ 14H
25 ~ 29OCH
2(CHCH
2) O, proportion 0.89.Said paracril is preferably nbr carboxyl terminal or hydroxy'terminated butadiene nitrile rubber, more preferably nbr carboxyl terminal.Wherein, said hydroxy'terminated butadiene nitrile rubber includes but not limited to YJ-82 and PolybdCN-15, and said nbr carboxyl terminal includes but not limited to CTBN1300X8, CTBN1072CG and CTBN1300X13.In the present invention, said toughner is preferably the mixture of AGE and the strange scholar's toughner of QS-H.
The present invention is a toughner with the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril; The main polymer chain molecule contains reactive group in the said toughner; Can react with the reactive group in the epoxy resin; Formation is that " island ", connection phase epoxy resin are " island structure " in " sea " with the main polymer chain disperse phase, thereby reaches toughness reinforcing purpose, shows as stretching, shearing resistance raising.Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether snappiness is good in the said toughner, and apolar surfaces is had wellability, can with urethane or paracril acting in conjunction, increase substantially stretching, the shearing resistance of the matrix material of follow-up formation.
In the present invention, said solidifying agent is indispensable component, and the consumption of said solidifying agent is the 50wt% ~ 100wt% of said epoxy resin composition, is preferably 75wt% ~ 80wt%.Being used for curing agent for epoxy resin generally has amine, anhydrides etc., and wherein, amine curing agent belongs to the self-vulcanizing system, is inappropriate for the resin system of gas cylinder; And acid anhydride type curing agent is the intermediate temperature setting system, and normal temperature for liquid, has good consistency with epoxy resin down, and process industrial art performance is good, is suitable for the resin system of gas cylinder.In the present invention, said solidifying agent is preferably methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride, more preferably methyl hexahydrophthalic anhydride.Said methyl tetrahydro phthalic anhydride (MTHPA) has fracture xanthochromia tendency because of containing a large amount of unsaturated double-bonds in curing and use, may be influential to product properties; Then there are not the problems referred to above in said methyl hexahydrophthalic anhydride (MHHPA), and application performance is preferable.
In the present invention, said curing catalyst is for quickening the material of curing reaction or reduction solidification value.The consumption of said curing catalyst is the 0.1wt% ~ 5.0wt% of said epoxy resin composition, is preferably 0.5wt% ~ 3.0wt%.Said curing catalyst is preferably three (dimethylamino methyl) phenol (DMP-30), benzyldimethylamine (BDMA) or trolamine, benzyldimethylamine more preferably, and its usage period and facilitation effect are preferable.
The present invention also provides a kind of preparation method who is used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder, may further comprise the steps:
With weight ratio is epoxy resin, thinner and the toughner mixing of 100:5 ~ 30:5 ~ 50; Obtain epoxy resin composition; Said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril, and the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 5;
With weight ratio is said epoxy resin composition, solidifying agent and the curing catalyst mixing of 100:50 ~ 100:0.1 ~ 5.0, obtains being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder.
It is consistent with content mentioned above that the present invention preparation is used for the raw material of composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder, gives unnecessary details no longer one by one at this.
In the present invention; Be that 100:5 ~ 30:5 ~ 50 add in the reactor drum according to weight ratio at first with epoxy resin, thinner and toughner; Said reactor drum is preferably the clean airtight reactor drum that has stirring, heating unit, obtains epoxy resin composition after preferably stirring;
Be that 100:50 ~ 100:0.1 ~ 5.0 add in the reactor drum with said epoxy resin composition, solidifying agent and curing catalyst according to weight ratio then; Said reactor drum is preferably the clean airtight reactor drum that has stirring, heating unit, obtains being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder after preferably stirring.
After obtaining being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder, the performance of its cured article is tested.Test result shows, the tensile strength >=60MPa of its cured article, and bending strength >=1165MPa, tension set >=4.5% shows that its cured article has the good mechanical performance.In addition, modest viscosity, the usage period of the said composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder are long, curing performance is excellent, has solved the problem of manufacturability aspect preferably, can satisfy requirements of large-scale production.
With the said composition epoxy resin impregnated glass fiber under constant temperature that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder; Send into drying tunnel and be heating and curing, obtain the winding layer matrix material, wherein; Condition of cure is: be heated to 80 ℃ earlier, insulation 2h ~ 3h; Reheat to 100 ℃ ~ 130 ℃, insulation 1h ~ 2h, promptly 80 ℃/(2h ~ 3h)+(100 ℃ ~ 130 ℃)/1h ~ 2h.After solidifying completion, the winding layer matrix material that obtains is carried out Performance Detection.According to CNS GB3354-82 " Test method for tensile properties of oriented fiber reinforced plastics ", the present invention measures the mechanical property of said winding layer matrix material.Test result shows that its tensile strength is more than 1333MPa, and interlaminar shear strength can reach 89.1MPa, promptly has mechanical property preferably, is beneficial to application.
Production technique according to CNG steel inner bag hoop winding gas cylinder; With said composition epoxy resin impregnated glass fiber, the winding gas cylinder under constant temperature that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder; Sending into drying tunnel is heating and curing; Condition of cure is identical with condition of cure mentioned above, obtains winding gas cylinder.The performance of gained winding gas cylinder satisfies the performance requriements of the international standard ISO11439:2000 " gasfueled vehicles on-board high-voltage gas cylinder " that CNS GB24160-2009 " compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder " and Organisme International de Normalisation pass through.
In order further to understand the present invention, the composition epoxy resin its preparation method that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder provided by the invention is described particularly below in conjunction with embodiment.
The performance index of the CYD-128 epoxy resin that following examples and comparative example are used are referring to table 1, and table 1 is the performance index of the used epoxy resin of the embodiment of the invention and comparative example.
The performance index of the CYD-128 epoxy resin that table 1 embodiment of the invention and comparative example are used
It is the benzyl glycidyl ether of XY692 that following examples and comparative example all adopt the trade mark, and its performance index are referring to table 2, and table 2 is the performance index of the used benzyl glycidyl ether of the embodiment of the invention and comparative example.
The performance index of the benzyl glycidyl ether that table 2 embodiment of the invention and comparative example are used
It is that the carbochain of XY748 is 12 ~ 14 alkyl glycidyl ether that following examples and comparative example all adopt the trade mark, and its performance index are referring to table 3, and table 3 is the performance index of 12 ~ 14 alkyl glycidyl ether for the embodiment of the invention and the used carbochain of comparative example.
The used carbochain of table 3 embodiment of the invention and comparative example is the performance index of 12 ~ 14 alkyl glycidyl ether
Embodiment 1
With 100kgCYD-128 epoxy resin, 10kg XY692 benzyl glycidyl ether, 15kg XY748 carbochain is that the strange scholar's toughner of 12 ~ 14 alkyl glycidyl ether, 3kgQS-H adds in the clean airtight reactor drum that has stirring, heating unit, obtains epoxy resin composition after stirring;
According to weight ratio is 100:66.4:0.625; Said epoxy resin composition, methyl hexahydrophthalic anhydride and benzyldimethylamine are added in the clean airtight reactor drum that has stirring, heating unit, obtain being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder after stirring.
Adopt the said composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder to prepare the winding layer matrix material according to method mentioned above, and measure its mechanical property according to method mentioned above.Test result shows that the interlaminar shear strength of said winding layer matrix material is 89.1MPa, and tensile strength is 1340MPa.
Embodiment 2
With 100kgE-51 epoxy resin, 15kgXY692 benzyl glycidyl ether, 15kgXY748 carbochain is that the strange scholar's toughner of 12 ~ 14 alkyl glycidyl ether, 5kgQS-H adds in the clean airtight reactor drum that has stirring, heating unit, obtains epoxy resin composition after stirring;
According to weight ratio is 100:75:1.0; Said epoxy resin composition, methyl hexahydrophthalic anhydride and benzyldimethylamine are added in the clean airtight reactor drum that has stirring, heating unit; Obtain being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder after stirring; The tensile strength of its cured article is 70MPa, and bending strength is 1265MPa, and tension set is 4.8%.
Adopt the said composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder to prepare the winding layer matrix material according to method mentioned above, and measure its mechanical property according to method mentioned above.Test result shows that the interlaminar shear strength of said winding layer matrix material is 65.6MPa, and tensile strength is 1394MPa.
Embodiment 3
With 100kgCYD-128 epoxy resin, 25kgXY692 benzyl glycidyl ether, 24kgXY748 carbochain is that the strange scholar's toughner of 12 ~ 14 alkyl glycidyl ether, 6kgQS-H adds in the clean airtight reactor drum that has stirring, heating unit, obtains epoxy resin composition after stirring;
According to weight ratio is 100:80.3:2.5; Said epoxy resin composition, methyl hexahydrophthalic anhydride and benzyldimethylamine are added in the clean airtight reactor drum that has stirring, heating unit, obtain being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder after stirring.
Adopt the said composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder to prepare the winding layer matrix material according to method mentioned above, and measure its mechanical property according to method mentioned above.Test result shows that the interlaminar shear strength of said winding layer matrix material is 65.1MPa, and tensile strength is 1333MPa.
Comparative example 1
In the clean airtight reactor drum that has stirring, heating unit, do not add the strange scholar's toughner of QS-H, and adding 18kg XY748 carbochain is 12 ~ 14 alkyl glycidyl ether, all the other contents are identical with embodiment 1, prepare composition epoxy resin.
Adopt said composition epoxy resin to prepare the winding layer matrix material according to embodiment 1 described method, and measure its mechanical property according to embodiment 1 described method.Test result shows that the interlaminar shear strength of said winding layer matrix material is 59.9MPa, and tensile strength is 1126MPa.
Comparative example 2
In the clean airtight reactor drum that has stirrings, heating unit, do not add the XY748 carbochain and be 12 ~ 14 alkyl glycidyl ether, and the strange scholar's toughner of adding 18kgQS-H, all the other contents are identical with embodiment 1, prepare composition epoxy resin.
Adopt said composition epoxy resin to prepare the winding layer matrix material according to embodiment 1 described method, and measure its mechanical property according to embodiment 1 described method.Test result shows that the interlaminar shear strength of said winding layer matrix material is 62.3MPa, and tensile strength is 1231MPa.
Can know by above embodiment and comparative example; The composition epoxy resin impregnated glass fiber that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder provided by the invention; Form matrix material through solidifying to wait; Its tensile strength is more than 1333MPa, and interlaminar shear strength can reach 89.1MPa, promptly has mechanical property preferably.
In addition; The composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder provided by the invention has that viscosity is low, working life is long, curing speed is evenly adjustable, exothermic peak is low, to characteristics such as spun glass wellability and construction technology are good, be beneficial to application.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. a composition epoxy resin that is used for compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder comprises epoxy resin composition, solidifying agent and curing catalyst that weight ratio is 100:50 ~ 100:0.1 ~ 5.0;
Said epoxy resin composition comprises epoxy resin, thinner and the toughner that weight ratio is 100:5 ~ 30:5 ~ 50;
Said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril, and the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 5.
2. composition epoxy resin according to claim 1 is characterized in that, the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 3.
3. composition epoxy resin according to claim 1 is characterized in that, said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether is that carbochain is 12 ~ 14 alkyl glycidyl ether.
4. composition epoxy resin according to claim 1 is characterized in that, said paracril is nbr carboxyl terminal or hydroxy'terminated butadiene nitrile rubber.
5. composition epoxy resin according to claim 1 is characterized in that, said epoxy resin composition comprises epoxy resin, thinner and the toughner that weight ratio is 100:10 ~ 20:10 ~ 30.
6. composition epoxy resin according to claim 1 is characterized in that, said thinner is n-butyl glycidyl ether, phenyl glycidyl ether or benzyl glycidyl ether.
7. composition epoxy resin according to claim 1 is characterized in that, comprises epoxy resin composition, solidifying agent and curing catalyst that weight ratio is 100:75 ~ 80:0.5 ~ 3.0.
8. composition epoxy resin according to claim 1 is characterized in that, said solidifying agent is methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride.
9. composition epoxy resin according to claim 1 is characterized in that, said curing catalyst is three (dimethylamino methyl) phenol, benzyldimethylamine or trolamine.
10. preparation method who is used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder may further comprise the steps:
With weight ratio is epoxy resin, thinner and the toughner mixing of 100:5 ~ 30:5 ~ 50; Obtain epoxy resin composition; Said toughner is the mixture of Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and urethane or paracril, and the weight ratio of said Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether and said urethane or paracril is 10:1 ~ 5;
With weight ratio is said epoxy resin composition, solidifying agent and the curing catalyst mixing of 100:50 ~ 100:0.1 ~ 5.0, obtains being used for the composition epoxy resin of compressed natural gas used as vehicle fuel steel inner bag hoop winding gas cylinder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210336261.1A CN102827457B (en) | 2012-09-12 | 2012-09-12 | Epoxy resin composition for automobile compressed natural gas steel inner liner ring-direction winding gas cylinder, and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210336261.1A CN102827457B (en) | 2012-09-12 | 2012-09-12 | Epoxy resin composition for automobile compressed natural gas steel inner liner ring-direction winding gas cylinder, and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102827457A true CN102827457A (en) | 2012-12-19 |
| CN102827457B CN102827457B (en) | 2015-04-29 |
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| CN201210336261.1A Expired - Fee Related CN102827457B (en) | 2012-09-12 | 2012-09-12 | Epoxy resin composition for automobile compressed natural gas steel inner liner ring-direction winding gas cylinder, and preparation method thereof |
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| CN (1) | CN102827457B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788648A (en) * | 2015-04-17 | 2015-07-22 | 大庆庆鲁朗润科技有限公司 | Modified solid epoxy resin with high glass transition temperature and high tenacity as well as preparation method thereof |
| CN105219046A (en) * | 2015-09-06 | 2016-01-06 | 江苏恒神股份有限公司 | Intermediate temperature setting is wound around resin and preparation method thereof, gained is wound around one-way slabs |
| CN109021898A (en) * | 2018-06-27 | 2018-12-18 | 湖北三江航天江北机械工程有限公司 | It is used to prepare the two-component toughening winding gas cylinder glue and preparation method thereof of compressed natural gas steel inner container hoop winding gas cylinder |
| CN113480962A (en) * | 2021-07-07 | 2021-10-08 | 上海库曜新材料有限公司 | Epoxy resin composition and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775893A (en) * | 2010-01-29 | 2010-07-14 | 嘉兴学院 | Epoxy floor material and installation construction method thereof |
-
2012
- 2012-09-12 CN CN201210336261.1A patent/CN102827457B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775893A (en) * | 2010-01-29 | 2010-07-14 | 嘉兴学院 | Epoxy floor material and installation construction method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788648A (en) * | 2015-04-17 | 2015-07-22 | 大庆庆鲁朗润科技有限公司 | Modified solid epoxy resin with high glass transition temperature and high tenacity as well as preparation method thereof |
| CN105219046A (en) * | 2015-09-06 | 2016-01-06 | 江苏恒神股份有限公司 | Intermediate temperature setting is wound around resin and preparation method thereof, gained is wound around one-way slabs |
| CN109021898A (en) * | 2018-06-27 | 2018-12-18 | 湖北三江航天江北机械工程有限公司 | It is used to prepare the two-component toughening winding gas cylinder glue and preparation method thereof of compressed natural gas steel inner container hoop winding gas cylinder |
| CN113480962A (en) * | 2021-07-07 | 2021-10-08 | 上海库曜新材料有限公司 | Epoxy resin composition and preparation method thereof |
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| CN102827457B (en) | 2015-04-29 |
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