CN109809740A - A kind of alkaline-resisting high temperature resistant thermosetting resin and its application - Google Patents
A kind of alkaline-resisting high temperature resistant thermosetting resin and its application Download PDFInfo
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- CN109809740A CN109809740A CN201910076235.1A CN201910076235A CN109809740A CN 109809740 A CN109809740 A CN 109809740A CN 201910076235 A CN201910076235 A CN 201910076235A CN 109809740 A CN109809740 A CN 109809740A
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- alkaline
- high temperature
- temperature resistant
- thermosetting resin
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Abstract
The invention belongs to resinoid bond technical fields, in particular to a kind of alkaline-resisting high temperature resistant thermosetting resin and its application, a kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component: 100 parts of bisphenol A type epoxy resin, 10~30 parts of phenol aldehyde type epoxy resin, 0.4~2 part of polyethylene terephthalate, 0.5~3 part of reinforcing fiber, 4~8 parts of silane coupling agent, 4~8 parts of curing agent, 0.5~2 part of curing accelerator, with good shock resistance, anti- folding effect, and volume shrinkage mass is small after solidifying, gel time is longer, in high temperature, performance does not change substantially under the working condition of highly basic, comprehensive performance is brilliant.
Description
Technical field
The invention belongs to resinoid bond technical field, in particular to a kind of alkaline-resisting high temperature resistant thermosetting resin and its answer
With.
Background technique
Resin/thyrite is prepared in the following way: silicon-carbide particle and thermosetting resin are mixed
After obtain castable, be then poured into molding mold, solidified in a certain temperature conditions, obtain resin/carbonization
Silicon ceramics, still, in castable, silicon-carbide particle is unevenly distributed or is easy layering, and the resin after solidification is filled in carbonization
Between silicon particle, bond effect is poor, causes resin/silicon carbide ceramics impact resistance, wearability poor；Existing resin/
Silicon carbide ceramics intensity in alkaline environment big, temperature is high can reduce, and be unable to satisfy the running environment of high temperature highly basic；For pouring
The mold of note, which requires, prevents adhesion and excellent sealing performance, and existing material and mold are difficult to prepare the biggish tree of volume
Rouge/silicon carbide ceramics.
Summary of the invention
The present invention to solve the above-mentioned problems, provides a kind of alkaline-resisting high temperature resistant thermosetting resin, have good shock resistance,
Anti- folding effect, and solidify after volume shrinkage mass it is small, gel time is longer, high temperature, highly basic working condition under performance substantially not
It changes, comprehensive performance is brilliant, also discloses the alkaline-resisting high temperature resistant thermosetting resin and is preparing resin/silicon carbide ceramics material
Application method in material.
The present invention is realized using following technical scheme:
A kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component:
Preferred scheme, the bisphenol-A shape epoxy resin are epoxy resin E54, E51, E44, E42, E35 or E31.
Preferred scheme, the curing agent are methylene diamine, aliphatic polyamine, high carbon number aliphatic diamine, Meng's alkane
One or more of diamines, cycloaliphatic amines.
Preferred scheme, the reinforcing fiber are one of glass fibre, aramid fiber, non-asbestos mineral fibres or several
Kind.
Preferred scheme, the silane coupling agent are phenyl trialkoxysilane, diphenyl dialkoxy silicane, methylbenzene
One or more of base dialkoxy silicane, triphenyl alkoxy silane.
Preferred scheme, the curing accelerator include benzyl dimethylamine, triethylenediamine, N, N '-dimethyl piperazine,
One of 2-ethyl-4-methylimidazole.
Preferred scheme, by weight, the curing accelerator further include 0.2~1 part of boric acid.
Preferred scheme, the reactive diluent are n-butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl
Glycerin ether or C12-14 alkyl glycidyl ether.
A kind of application of alkaline-resisting high temperature resistant thermosetting resin as described above, is to prepare resin/silicon carbide ceramics, prepare
Process includes the following steps:
S1 is stirred evenly after mixing following substances in parts by weight, and solidifying substance is made
S2 solidifies solidifying substance under the conditions of 70~150 DEG C, and curing time is 1~3h, and resin/silicon carbide is made
Ceramics.
Preferred scheme, the silicon-carbide particle are gradation silicon-carbide particle, by weight, the group including following partial size
Point:
The beneficial effects of the present invention are:
1, the present invention expects based on selecting bisphenol A type epoxy resin, with phenol aldehyde type epoxy resin and poly terephthalic acid
Second diester is used in compounding, and is solidified and is cross-linked to form stable cured product, after tested, under the conditions of 110 DEG C, mass concentration 45%
NaOH solution working condition under, properties characterization is good.
2, polyethylene terephthalate of the invention and reinforcing fiber improve the rigidity of cured product, abrasion resistant effect and
Fatigue resistance, using the silane coupling agent containing phenyl series, itself has preferable heat resistance, can be used as inorganic-organic company
Agent use is connect, the bonding strength between alkaline-resisting fire resistant resin, reinforcing fiber, curing accelerator and silicon-carbide particle is improved,
In resin/silicon carbide ceramics resin phase, curing accelerator effectively increases the stability and tear-resistant effect of cured product,
Reinforcing fiber improves the intensity of resin phase, and resin/silicon carbide ceramics flexural strength is greatly improved, impact, resistance to
Mill property is preferable, can prepare the biggish resin/silicon carbide ceramics of volume, use suitable for some special application scenarios.
3, the present invention by adding boric acid into slurry, solidifying substance it is cured during, with alkaline-resisting high temperature resistant thermosetting
Property resin in other component reactions, cured product formed the three-dimensional cross-linked reticular structure containing boron atom, cooperate it is silane coupled
Phenyl isoreactivity group in agent, so that the high temperature resistance of product has obtained biggish promotion, the volatilization before solidification, in slurry
Object content is few, low using reactive diluent improvement viscosity, and bubble, resistance to abrasion and intensity are not present in the resin phase being formed by curing
It is higher.
4, the curing accelerator selected of the present invention can effectively shorten solidification temperature and curing time, and room temperature gel time is big
It in 2.5h, is very suitable to needed for actual production, resin/silicon carbide ceramics obtained is in friction, due to there is gold in resin phase
Belong to atomic nucleus, reinforcing fiber and itself existing cross-linked structure, resin/silicon carbide ceramics wearability and fracture elongation
It is greatly improved.
Specific embodiment
The technical solution in embodiment will be clearly and completely described below.Obviously, described embodiment is only
It is a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiment of the present invention, ordinary skill people
Member's every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component:
Resin/silicon carbide ceramics is prepared using the alkaline-resisting high temperature resistant thermosetting resin of the present embodiment, preparation process includes such as
Lower step:
S1 weighs epoxy resin E51, phenol aldehyde type epoxy resin, polyethylene terephthalate, the glass of above-mentioned parts by weight
Fiber, phenyl trialkoxysilane, ethylenediamine, benzyl dimethylamine and n-butyl glycidyl ether, the carbon for being 1~3mm with partial size
It is stirred evenly after 500 parts of silicon carbide particle mixing, solidifying substance is made；
S2 solidifies solidifying substance under the conditions of 120 DEG C, curing time 3h, and resin/silicon carbide ceramics is made.
Embodiment 2
A kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component:
Resin/silicon carbide ceramics is prepared using the alkaline-resisting high temperature resistant thermosetting resin of the present embodiment, preparation process includes such as
Lower step:
S1, weigh the epoxy resin E44 of above-mentioned parts by weight, phenol aldehyde type epoxy resin, polyethylene terephthalate, without stone
Cotton mineral fibres, methyl phenyl di-alkoxy silane, m-xylene diamine, high carbon number aliphatic diamine, triethylenediamine and
Phenyl glycidyl ether, with partial size be 600 parts of silicon-carbide particle of 1~3mm mix after stir evenly, obtained solidifying substance；
S2 solidifies solidifying substance under the conditions of 70 DEG C, curing time 3h, and resin/silicon carbide ceramics is made.
Embodiment 3
A kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component:
Resin/silicon carbide ceramics is prepared using the alkaline-resisting high temperature resistant thermosetting resin of the present embodiment, preparation process includes such as
Lower step:
S1 weighs epoxy resin E31, phenol aldehyde type epoxy resin, polyethylene terephthalate, the aramid fiber of above-mentioned parts by weight
Fiber, diphenyl dialkoxy silicane, diethylenetriamine, N, N '-dimethyl piperazine, boric acid and allyl glycidyl ether, with
It is stirred evenly after 700 parts of gradation silicon-carbide particle mixing, solidifying substance is made；
S2 solidifies solidifying substance under the conditions of 100 DEG C, curing time 2h, and resin/silicon carbide ceramics, institute is made
Stating resin/silicon carbide ceramics diameter is 2m.
In the present embodiment, in the gradation silicon-carbide particle, by weight, the silicon-carbide particle including following partial size:
Embodiment 4
A kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component:
Resin/silicon carbide ceramics is prepared using the alkaline-resisting high temperature resistant thermosetting resin of the present embodiment, preparation process includes such as
Lower step:
S1 weighs epoxy resin E35, epoxy resin E54, phenol aldehyde type epoxy resin, the poly- terephthaldehyde of above-mentioned parts by weight
Sour second diester, glass fibre, aramid fiber, diphenyl dialkoxy silicane, methyl phenyl di-alkoxy silane, the bis- (ammonia of 1,3-
Methyl) hexamethylene, triethylene tetramine, benzyl dimethylamine, 2 ethyl hexanoic acid yttrium, boric acid, C12-14 alkyl glycidyl ether, allyl
Base glycidol ether stirs evenly after mixing with 550 parts of gradation silicon-carbide particle, and solidifying substance is made；
S2 solidifies solidifying substance under the conditions of 150 DEG C, curing time 1.5h, and resin/silicon carbide ceramics is made.
In the present embodiment, in the gradation silicon-carbide particle, by weight, the silicon-carbide particle including following partial size:
Embodiment 5
A kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component:
Resin/silicon carbide ceramics is prepared using the alkaline-resisting high temperature resistant thermosetting resin of the present embodiment, preparation process includes such as
Lower step:
S1 weighs epoxy resin E42, epoxy resin E51, phenol aldehyde type epoxy resin, the poly- terephthaldehyde of above-mentioned parts by weight
Sour second diester, glass fibre, non-asbestos mineral fibres, phenyl trialkoxysilane, methyl phenyl di-alkoxy silane, Meng's alkane two
Amine, triethylene tetramine, benzyl dimethylamine, 2-ethyl-4-methylimidazole, boric acid, C12-14 alkyl glycidyl ether and normal-butyl
Glycidol ether stirs evenly after mixing with 650 parts of gradation silicon-carbide particle, and solidifying substance is made；
S2 solidifies solidifying substance under the conditions of 90 DEG C, curing time 2.5h, and resin/silicon carbide ceramics is made.
In the present embodiment, in the gradation silicon-carbide particle, by weight, the silicon-carbide particle including following partial size:
Comparative example 1
A kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component:
Resin/silicon carbide ceramics is prepared using the alkaline-resisting high temperature resistant thermosetting resin of the present embodiment, preparation process includes such as
Lower step:
S1 weighs epoxy resin E51, phenol aldehyde type epoxy resin, polyethylene terephthalate, the glass of above-mentioned parts by weight
Fiber, phenyl trialkoxysilane, ethylenediamine, benzyl dimethylamine and n-butyl glycidyl ether, the carbon for being 1~3mm with partial size
It is stirred evenly after 600 parts of silicon carbide particle mixing, solidifying substance is made；
S2 solidifies solidifying substance under the conditions of 90 DEG C, curing time 2h, and silicon carbide ceramics is made.
Comparative example 2
A kind of alkaline-resisting high temperature resistant thermosetting resin, by weight, including following component:
Resin/silicon carbide ceramics is prepared using the alkaline-resisting high temperature resistant thermosetting resin of the present embodiment, preparation process includes such as
Lower step:
S1 weighs epoxy resin E51, phenol aldehyde type epoxy resin, polyethylene terephthalate, the glass of above-mentioned parts by weight
Fiber, phenyl trialkoxysilane, ethylenediamine, benzyl dimethylamine and n-butyl glycidyl ether, with gradation silicon-carbide particle 550
It is stirred evenly after part mixing, solidifying substance is made；
S2 solidifies solidifying substance under the conditions of 150 DEG C, curing time 2h, and resin/silicon carbide ceramics, institute is made
Stating resin/silicon carbide ceramics diameter is 2m.
In the present embodiment, in the gradation silicon-carbide particle, by weight, the silicon-carbide particle including following partial size:
Testing example 1~5, the performance of alkaline-resisting fire resistant resin in comparative example 1~2, obtains the performance parameter such as table 1:
The performance parameter of the alkaline-resisting fire resistant resin of table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Fracture elongation, % | 7.2 | 7.4 | 7.6 | 7.7 | 7.7 | 4.8 | 6.8 |
| Cubical contraction, % | 3.6 | 3.4 | 3.5 | 3.2 | 3.3 | 4.2 | 4.4 |
| Heat distortion temperature, >= | 135℃ | 135℃ | 135℃ | 135℃ | 135℃ | 135℃ | 135℃ |
| Gel time (25 DEG C), >= | 2.5h | 3h | 3h | 3h | 3h | 2.5h | 2.5h |
2 resins of table/silicon carbide ceramics strength at normal temperature
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Strength at normal temperature, MPa | 82.3 | 83.3 | 85.2 | 88.3 | 87.9 | 43.8 | 56.4 |
Wherein, test method is as follows: 1, fracture elongation is tested referring to GB/T2568-1995；2, volume contraction
Rate is tested using water leaching method；3, strength at normal temperature is tested referring to GB/T3001-2007.
In order to further test the characteristic of the alkaline-resisting fire resistant resin, above-mentioned alkaline-resisting fire resistant resin is subjected to alkaline-resisting survey
Examination, testing scheme are as follows: under the conditions of 110 DEG C, alkaline-resisting fire resistant resin obtained is soaked in the NaOH that mass concentration is 45%
Immersion treatment 4h, 8h in solution, test fracture elongation obtain the performance parameter such as table 2:
Performance parameter after the alkaline-resisting Soak Test 4h of table 2
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| 4h fracture elongation, % | 7.2 | 7.4 | 7.6 | 7.7 | 7.6 | 4.8 | 6.8 |
| 8h fracture elongation, % | 7.2 | 7.4 | 7.6 | 7.6 | 7.7 | 3.6 | 4.3 |
Further, resin/silicon carbide ceramics obtained is soaked in the NaOH solution that mass concentration is 45% and is impregnated
4h, 8h are handled, test fracture elongation obtains the performance parameter such as table 3:
3 resins of table/silicon carbide ceramics strength at normal temperature
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Strength at normal temperature, MPa | 82.3 | 83.3 | 85.2 | 88.3 | 87.9 | 39.8 | 52.1 |
By above-mentioned test result it is found that the alkaline-resisting fire resistant resin has good shock resistance, anti-folding effect, and after solidification
Volume shrinkage mass is small, and gel time is longer, high temperature, highly basic working condition under performance do not change substantially, comprehensive performance
It is brilliant.
Claims (10)
1. a kind of alkaline-resisting high temperature resistant thermosetting resin, which is characterized in that by weight, including following component:
2. alkaline-resisting high temperature resistant thermosetting resin according to claim 1, it is characterised in that: the bisphenol-A shape epoxy resin
For epoxy resin E54, E51, E44, E42, E35 or E31.
3. alkaline-resisting high temperature resistant thermosetting resin according to claim 1, it is characterised in that: the curing agent is methylene two
One of amine, aliphatic polyamine, fatty amine containing aromatic rings, high carbon number aliphatic diamine, Meng's alkane diamines, cycloaliphatic amines are several
Kind.
4. alkaline-resisting high temperature resistant thermosetting resin according to claim 1, it is characterised in that: the reinforcing fiber is glass fibers
One or more of dimension, aramid fiber, non-asbestos mineral fibres.
5. alkaline-resisting high temperature resistant thermosetting resin according to claim 1, it is characterised in that: the silane coupling agent is phenyl
One of trialkoxy silane, diphenyl dialkoxy silicane, methyl phenyl di-alkoxy silane, triphenyl alkoxy silane
Or it is several.
6. alkaline-resisting high temperature resistant thermosetting resin according to claim 1, it is characterised in that: the curing accelerator includes benzyl
Base dimethylamine, triethylenediamine, N, one of N '-dimethyl piperazine, 2-ethyl-4-methylimidazole.
7. alkaline-resisting high temperature resistant thermosetting resin according to claim 6, it is characterised in that: by weight, the solidification
Promotor further includes 0.2~1 part of boric acid.
8. alkaline-resisting high temperature resistant thermosetting resin according to claim 1, it is characterised in that: the reactive diluent is positive fourth
Base glycidol ether, allyl glycidyl ether, phenyl glycidyl ether or C12-14 alkyl glycidyl ether.
9. a kind of application of alkaline-resisting high temperature resistant thermosetting resin as described in claim 1, which is characterized in that including walking as follows
It is rapid:
S1 is stirred evenly after mixing following substances in parts by weight, and solidifying substance is made
S2 solidifies solidifying substance under the conditions of 70~150 DEG C, and curing time is 1~3h, and resin/silicon carbide pottery is made
Porcelain.
10. the application of alkaline-resisting high temperature resistant thermosetting resin according to claim 9, which is characterized in that the silicon carbide
Grain is gradation silicon-carbide particle, by weight, the component including following partial size:
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417804A (en) * | 2010-09-28 | 2012-04-18 | 比亚迪股份有限公司 | Adhesive, its preparation method and application method |
| CN102925091A (en) * | 2012-10-10 | 2013-02-13 | 江苏新誉重工科技有限公司 | High-strength high-toughness epoxy resin adhesive and preparation method thereof |
| CN106916413A (en) * | 2015-12-24 | 2017-07-04 | 比亚迪股份有限公司 | A kind of composition epoxy resin and preparation method thereof, fiber resin composite material, aluminium/fiber/resin composite |
| CN108148353A (en) * | 2017-12-27 | 2018-06-12 | 惠柏新材料科技（上海）股份有限公司 | A kind of composition epoxy resin |
-
2019
- 2019-01-26 CN CN201910076235.1A patent/CN109809740B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417804A (en) * | 2010-09-28 | 2012-04-18 | 比亚迪股份有限公司 | Adhesive, its preparation method and application method |
| CN102925091A (en) * | 2012-10-10 | 2013-02-13 | 江苏新誉重工科技有限公司 | High-strength high-toughness epoxy resin adhesive and preparation method thereof |
| CN106916413A (en) * | 2015-12-24 | 2017-07-04 | 比亚迪股份有限公司 | A kind of composition epoxy resin and preparation method thereof, fiber resin composite material, aluminium/fiber/resin composite |
| CN108148353A (en) * | 2017-12-27 | 2018-06-12 | 惠柏新材料科技（上海）股份有限公司 | A kind of composition epoxy resin |
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