CN105440584A - Low-shrinkage epoxy resin system and preparation method thereof - Google Patents
Low-shrinkage epoxy resin system and preparation method thereof Download PDFInfo
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- CN105440584A CN105440584A CN201510917668.7A CN201510917668A CN105440584A CN 105440584 A CN105440584 A CN 105440584A CN 201510917668 A CN201510917668 A CN 201510917668A CN 105440584 A CN105440584 A CN 105440584A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Epoxy Resins (AREA)
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Abstract
The invention provides a low-shrinkage epoxy resin system and a preparation method thereof. The low-shrinkage epoxy resin system comprises, by weight, 90 to 110 parts of bisphenol A type epoxy resin, 15 to 25 parts of an epoxy diluent, 40 to 60 parts of a curing agent, 1 to 3 parts of a coupling agent and 4 to 7 parts of nanometer barium titanate powder. Compared with matrix resin, low-shrinkage epoxy resin obtained in the invention has the following advantages: a shrinkage rate is reduced by 50%; mechanical properties of epoxy resin are not changed; and the low-shrinkage epoxy resin is applicable in a severe working environment and to a structural member with a high requirement on dimensional stability.
Description
Technical field
The present invention relates to a kind of low shrinkage epoxy resin system and preparation method thereof.
Background technology
Epoxy resin is due to its good cohesiveness, thermotolerance, chemical proofing and mechanical property, it is the kind that in thermosetting resin, application quantity is maximum, but cause structure both shrinks because epoxy resin, in curing cross-linked process, addition reaction occurs, give in work under bad environment, application on the structural part that dimensional stability requirements is higher brings certain unfavorable, especially in the structural part of high stable, resin system shrinks the excessive structural part profile precision that causes and changes, and then affect the result of use of product, therefore the shrinking percentage in epoxy-resin systems solidification process must be reduced.
Summary of the invention
For defect of the prior art, the object of this invention is to provide a kind of low shrinkage epoxy resin system and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
The invention provides a kind of low shrinkage epoxy resin system, it is characterized in that, comprise each component of following parts by weight:
Preferably, described low shrinkage epoxy resin system comprises each component of following parts by weight:
Preferably, described bisphenol A type epoxy resin is E-51 epoxy resin.
Preferably, the median size of described nano barium carbonate powder is 100 ~ 150nm.
Preferably, described coupling agent is titanic acid ester system coupling agent.
The present invention carries out surface treatment by coupling agent to barium carbonate powder, improves the dispersion effect of barium titanate.Adopting nano level barium carbonate powder, the shrinking percentage of resin matrix can be reduced when adding less amount.
Preferably, described solidifying agent is anhydride curing agent; Preferred, anhydride curing agent is Tetra Hydro Phthalic Anhydride.
Preferably, described epoxide diluent comprises butylglycidyl ether, 1, one or more in 4-butanediol diglycidyl ether, ethylene glycol diglycidylether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, fatty glycidyl ether, benzyl glycidyl ether, 1,6-hexanediol diglycidyl ether, propylene oxide o-cresyl ether or o-tolyl glycidyl ether, neopentylglycol diglycidyl ether.Epoxide diluent can reduce epoxy resin solidifying system viscosity, increases mobility.
Present invention also offers a kind of preparation method of low shrinkage epoxy resin system, described preparation method comprises the steps:
S1, each composition weight number according to claim 1 take raw material;
S2, coupling agent, nano barium carbonate powder are joined stirring reaction in anhydride curing agent, then carry out supersound process, then the reactant a obtained is left standstill;
S3, bisphenol A type epoxy resin is mixed with epoxide diluent after stir, obtain mixture b;
S4, by step S2 obtain reactant a mix with the mixture b that step S3 obtains, carry out stirring and supersound process simultaneously, obtain described low shrinkage epoxy resin system.
Preferably, in step 2, described mixing speed is 2000 ~ 4000 turns/min, and the time is 5 ~ 10min; Described sonication treatment time is 60 ~ 90min; Described time of repose is 12 ~ 24h.
Preferably, in step 3, described mixing speed is 2000 ~ 4000 turns/min, and the time is 30 ~ 60min; In step 4, the time of described stirring and supersound process is 60 ~ 90min, and mixing speed is 2000 ~ 4000 turns/min.
The present invention is mixed by nano barium phthalate and coupling agent, improves the dispersion effect of barium titanate, improves the effect of barium carbonate powder, reduce the shrinking percentage of epoxy resin.
Compared with prior art, the present invention has following beneficial effect:
(1) the epoxy-resin systems shrinking percentage in the curing process of the present invention's acquisition is low, compared with bulk resin, reduces 50%.
(2), after adding powder, the mechanical property of epoxy resin does not change.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
Present embodiments provide a kind of low shrinkage epoxy resin system, its each component and parts by weight as shown in table 1.Its preparation method comprises the following steps:
For subsequent use after carrying out mechanical stirring (rotating speed 2000 turns/min) 30min after getting bisphenol A type epoxy resin E-51100 part, epoxide diluent propylene oxide o-cresyl ether 20 parts mixing;
Get 50 parts of Tetra Hydro Phthalic Anhydrides, titanate coupling agent 2 parts, nano barium carbonate powder (median size 100nm) 5 parts, mechanical stirring 5min after mixing, after then carrying out sonic oscillation 60min, in vacuum drying oven, leave standstill 24 hours;
Carrying out mechanical stirring by carrying out ultrasonic vibration 60min after the above-mentioned two kinds of liquid mixing mixed simultaneously, putting into refrigerator after having mixed and storing for subsequent use.
embodiment 2
Present embodiments provide a kind of low shrinkage epoxy resin system, its each component and parts by weight as shown in table 1.Its preparation method comprises the following steps:
For subsequent use after carrying out mechanical stirring (rotating speed 4000 turns/min) 40min after getting bisphenol A type epoxy resin E-5190 part, epoxide diluent butylglycidyl ether 15 parts mixing;
Get 40 parts of Tetra Hydro Phthalic Anhydrides, titanate coupling agent 1 part, nano barium carbonate powder (median size 100nm) 4 parts, mechanical stirring 10min after mixing, after then carrying out sonic oscillation 60min, in vacuum drying oven, leave standstill 18 hours;
Carrying out mechanical stirring by carrying out ultrasonic vibration 60min after the above-mentioned two kinds of liquid mixing mixed simultaneously, putting into refrigerator after having mixed and storing for subsequent use.
embodiment 3
Present embodiments provide a kind of low shrinkage epoxy resin system, its each component and parts by weight as shown in table 1.Its preparation method comprises the following steps:
For subsequent use after carrying out mechanical stirring (rotating speed 2000 turns/min) 30min after getting bisphenol A type epoxy resin E-51110 part, thinner propylene oxide o-cresyl ether 25 parts mixing;
Get 60 parts of Tetra Hydro Phthalic Anhydrides, titanate coupling agent 3 parts, nano barium carbonate powder (median size 100nm) 7 parts, mechanical stirring 5min after mixing, after then carrying out sonic oscillation 90min, in vacuum drying oven, leave standstill 12 hours;
Carrying out mechanical stirring by carrying out ultrasonic vibration 90min after the above-mentioned two kinds of liquid mixing mixed simultaneously, putting into refrigerator after having mixed and storing for subsequent use.
comparative example 1
This comparative example provides a kind of epoxy-resin systems, its each component and parts by weight as shown in table 1.Its preparation method comprises the following steps:
For subsequent use after carrying out mechanical stirring (rotating speed 2000 turns/min) 30min after getting bisphenol A type epoxy resin E-51100 part, epoxide diluent propylene oxide o-cresyl ether 20 parts mixing;
Get 50 parts of Tetra Hydro Phthalic Anhydrides, nano barium carbonate powder (median size 100nm) 5 parts, mechanical stirring 5min after mixing, after then carrying out sonic oscillation 60min, in vacuum drying oven, leave standstill 24 hours;
Carrying out mechanical stirring by carrying out ultrasonic vibration 60min after the above-mentioned two kinds of liquid mixing mixed simultaneously, putting into refrigerator after having mixed and storing for subsequent use.
comparative example 2
This comparative example provides a kind of epoxy-resin systems, its each component and parts by weight as shown in table 1.Its preparation method comprises the following steps:
For subsequent use after carrying out mechanical stirring (rotating speed 2000 turns/min) 30min after getting bisphenol A type epoxy resin E-51100 part, epoxide diluent propylene oxide o-cresyl ether 20 parts mixing;
Get 50 parts of Tetra Hydro Phthalic Anhydrides, titanate coupling agent 2 parts, nano barium carbonate powder (median size 100nm) 2 parts, mechanical stirring 5min after mixing, after then carrying out sonic oscillation 60min, in vacuum drying oven, leave standstill 24 hours;
Carrying out mechanical stirring by carrying out ultrasonic vibration 60min after the above-mentioned two kinds of liquid mixing mixed simultaneously, putting into refrigerator after having mixed and storing for subsequent use.
comparative example 3
This comparative example provides a kind of epoxy-resin systems, its each component and parts by weight as shown in table 1.Its preparation method comprises the following steps:
For subsequent use after carrying out mechanical stirring (rotating speed 2000 turns/min) 30min after getting bisphenol A type epoxy resin E-51110 part, epoxide diluent propylene oxide o-cresyl ether 25 parts mixing;
Get 60 parts of Tetra Hydro Phthalic Anhydrides, titanate coupling agent 3 parts, nano barium carbonate powder (median size 100nm) 9 parts, mechanical stirring 5min after mixing, after then carrying out sonic oscillation 60min, in vacuum drying oven, leave standstill 24 hours;
Carrying out mechanical stirring by carrying out ultrasonic vibration 60min after the above-mentioned two kinds of liquid mixing mixed simultaneously, putting into refrigerator after having mixed and storing for subsequent use.
comparative example 4
This comparative example provides a kind of epoxy-resin systems, its each component and parts by weight as shown in table 1.Its preparation method comprises the following steps:
For subsequent use after carrying out mechanical stirring (rotating speed 4000 turns/min) 40min after getting bisphenol A type epoxy resin E-5190 part, epoxide diluent butylglycidyl ether 15 parts mixing;
Get 40 parts of Tetra Hydro Phthalic Anhydrides, titanate coupling agent 1 part, nano barium carbonate powder (median size 100nm) 4 parts, mechanical stirring 30min after mixing, then in vacuum drying oven, leave standstill 24 hours;
Carry out mechanical stirring 60min by after the above-mentioned two kinds of liquid mixing mixed, put into refrigerator after having mixed and store for subsequent use.
Each component and parts by weight thereof in table 1 embodiment 1-3 and comparative example 1-4
Effectiveness comparison:
The detected result of epoxy-resin systems prepared by embodiment 1-3 and comparative example 1-4 is as shown in table 2.
Table 2
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. a low shrinkage epoxy resin system, is characterized in that, comprises each component of following parts by weight:
2. low shrinkage epoxy resin system as claimed in claim 1, is characterized in that, comprise each component of following parts by weight:
3. low shrinkage epoxy resin system as claimed in claim 1, it is characterized in that, described bisphenol A type epoxy resin is E-51 epoxy resin.
4. low shrinkage epoxy resin system as claimed in claim 1, it is characterized in that, the median size of described nano barium carbonate powder is 100 ~ 150nm.
5. low shrinkage epoxy resin system as claimed in claim 1, it is characterized in that, described coupling agent is titanic acid ester system coupling agent.
6. low shrinkage epoxy resin system as claimed in claim 1, it is characterized in that, described solidifying agent is acid anhydride type curing agent.
7. low shrinkage epoxy resin system as claimed in claim 1, it is characterized in that, described epoxide diluent comprises butylglycidyl ether, 1, one or more in 4-butanediol diglycidyl ether, ethylene glycol diglycidylether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, fatty glycidyl ether, benzyl glycidyl ether, 1,6-hexanediol diglycidyl ether, propylene oxide o-cresyl ether or o-tolyl glycidyl ether, neopentylglycol diglycidyl ether.
8. the preparation method of low shrinkage epoxy resin system as claimed in claim 1, it is characterized in that, described preparation method comprises the steps:
S1, each composition weight number according to claim 1 take raw material;
S2, coupling agent, nano barium carbonate powder are joined stirring reaction in anhydride curing agent, then carry out supersound process, then the reactant a obtained is left standstill;
S3, bisphenol A type epoxy resin is mixed with epoxide diluent after stir, obtain mixture b;
S4, by step S2 obtain reactant a mix with the mixture b that step S3 obtains, carry out stirring and supersound process simultaneously, obtain described low shrinkage epoxy resin system.
9. the preparation method of low shrinkage epoxy resin system as claimed in claim 8, it is characterized in that, in step S2, described mixing speed is 2000 ~ 4000 turns/min, and the time is 5 ~ 10min; Described sonication treatment time is 60 ~ 90min; Described time of repose is 12 ~ 24h.
10. the preparation method of low shrinkage epoxy resin system as claimed in claim 8, it is characterized in that, in step S3, described mixing speed is 2000 ~ 4000 turns/min, and the time is 30 ~ 60min; In step S4, the time of described stirring and supersound process is 60 ~ 90min, and mixing speed is 2000 ~ 4000 turns/min.
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Cited By (2)
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| CN109880565A (en) * | 2019-03-12 | 2019-06-14 | 中国石油大学(华东) | A kind of limestone deep-well stabilizing borehole rubber plug and preparation method thereof |
| CN111825954A (en) * | 2020-06-30 | 2020-10-27 | 上海复合材料科技有限公司 | Normal-temperature curing resin system for copying antenna reflecting surface and preparation method thereof |
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| CN111825954A (en) * | 2020-06-30 | 2020-10-27 | 上海复合材料科技有限公司 | Normal-temperature curing resin system for copying antenna reflecting surface and preparation method thereof |
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| CN105440584B (en) | 2017-12-15 |
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