CN100552126C - A kind of fire resistant pnenolic aldehyde type fiber finish and preparation method thereof - Google Patents
A kind of fire resistant pnenolic aldehyde type fiber finish and preparation method thereof Download PDFInfo
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- CN100552126C CN100552126C CNB2007101448975A CN200710144897A CN100552126C CN 100552126 C CN100552126 C CN 100552126C CN B2007101448975 A CNB2007101448975 A CN B2007101448975A CN 200710144897 A CN200710144897 A CN 200710144897A CN 100552126 C CN100552126 C CN 100552126C
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- catalyst
- fire resistant
- type fiber
- aldehyde type
- weight portions
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Abstract
A kind of fire resistant pnenolic aldehyde type fiber finish and preparation method thereof, it relates to a kind of fibre finish and preparation method thereof.The invention solves present quartz fibre and strengthen high performance resin based composite material interface that poly-aryl ethane (PAA) and other main chain contain fragrant heterocycle in conjunction with poor, high temperature produces problems such as bubble.Product of the present invention adds ethyl acetate solvent after by phenol, formaldehyde reaction again and is mixed with solution and forms, and its preparation method is as follows: one, get phenol and formaldehyde, add catalyst A, react 4h under 80～100 ℃ of conditions; Two, add catalyst B again, under 100 ℃ of conditions, react 1～2h; Three, add catalyst C again, dissolving back decompression distillation fully; Add the ethyl acetate wiring solution-forming.High-performance composite materials after the product treatment of the present invention can use under 450～500 ℃ hot conditions, eliminate high temperature bubbling phenomenon.With respect to the composite without finishing agent of the present invention, the normal temperature interlaminar shear strength after product treatment of the present invention has improved more than 50%.
Description
Technical field
The present invention relates to a kind of fibre finish and preparation method thereof.
Background technology
Along with under development in science and technology and the harsh and unforgiving environments to the requirement of material property, emerge a large amount of high performance resins, poly-aryl ethane (PAA) and modified resin thereof are the novel high performance resins of a class, and these high polymers just have excellent heat resisting, are mainly used in the Aero-Space high-tech sector.
Quartz fibre strengthens poly-aryl ethane (PAA) and the modified resin based composites is the high-performance composite materials that a kind of high temperature uses, but thermal decomposition can take place and produce bubble when using under 500 ℃ hot conditions, this destruction occurs in composite material interface and resin inside, cause the composite bubbling, mechanical property significantly descends, and has limited its serviceability temperature.
Summary of the invention
It is poor to the objective of the invention is in order to solve poly-aryl ethane (PAA) of quartz fibre enhancing and modified resin based composite material interface adhesion thereof, and high temperature produces problems such as bubble, and a kind of fire resistant pnenolic aldehyde type fiber finish and preparation method thereof is provided.The present invention is directed to the design feature and the curing cross-linking reaction mode of poly-aryl ethane (PAA) and modified resin thereof, fiber is carried out surface modification, and realized between poly-aryl ethane (PAA) and modified resin and fiber, having formed the boundary layer that is complementary, form the boundary strength that chemical bond improves composite between itself and fiber thereby make, give full play to the high-fire resistance of fortifying fibre and poly-aryl ethane (PAA) and modified resin matrix excellence thereof; And the following micromolecule that can absorb poly-aryl ethane (PAA) and modified resin thermal decomposition generation thereof of high temperature, eliminate high temperature bubbling phenomenon, thereby improve its serviceability temperature.
Fire resistant pnenolic aldehyde type fiber finish of the present invention is to add ethyl acetate solvent in 100～110 weight portion phenol and the reacted product of 115～135 parts by weight of formaldehyde to be mixed with weight percent concentration be that the ethyl acetate solution of 70～80% phenolic resins forms, the catalyst A of 2～3 weight portions, the catalyst B of 10～15 weight portions and the catalyst C of 10～12 weight portions have been used in the reaction of phenol and formaldehyde, wherein catalyst A is made up of by 1: 1: 1 weight ratio ZnO, NaOH and KOH, and catalyst B is by Al
2(SO
4)
3, AlCl
3And FeCl
3Form by 1: 1: 1 weight ratio, catalyst C is by Ti (OC
4H
9)
4, ethyl orthosilicate and borate form by 2: 1: 1 weight ratio.
The preparation method of above-mentioned fire resistant pnenolic aldehyde type fiber finish is realized by following reaction: one, get 100～110 weight portion phenol and 115～135 parts by weight of formaldehyde and add reactor, the catalyst A that in reactor, adds 2～3 weight portions again, catalyst A is made up of by 1: 1: 1 weight ratio ZnO, NaOH and KOH, reacts 4h then under 80～100 ℃ of conditions; Two, the catalyst B that adds 10～15 weight portions in reaction vessel again, catalyst B are by Al
2(SO
4)
3, AlCl
3And FeCl
3Form by 1: 1: 1 weight ratio, under 100 ℃ of conditions, react 1～2h then; Three, the catalyst C that adds 10～12 weight portions in reactor again, catalyst C are by Ti (OC
4H
9)
4, ethyl orthosilicate and borate form by 2: 1: 1 weight ratio, treat to carry out decompression distillation after catalyst C dissolves fully; When reaction system is decompressed to 120 ℃, stop decompression distillation, add ethyl acetate solvent simultaneously and be mixed with the ethyl acetate solution that weight percent concentration is 70～80% phenolic resins; Promptly obtain fire resistant pnenolic aldehyde type fiber finish.
Composite after the product treatment of the present invention can use under 500 ℃ hot conditions.With respect to composite without finishing agent of the present invention, interlaminar shear strength after product treatment of the present invention has improved more than 50%, and its compressive strength has improved more than 25%, the compression amount of touching has improved more than 29.5%, TENSILE STRENGTH has improved more than 35.2%, and stretch modulus has improved more than 12.2%; And the dielectric properties of composite also improve.
The specific embodiment
The specific embodiment one: the fire resistant pnenolic aldehyde type fiber finish of present embodiment is to add ethyl acetate solvent in 100～110 weight portion phenol and the reacted product of 115～135 parts by weight of formaldehyde to be mixed with weight percent concentration be that the ethyl acetate solution of 70～80% phenolic resins forms, the catalyst A of 2～3 weight portions, the catalyst B of 10～15 weight portions and the catalyst C of 10～12 weight portions have been used in the reaction of phenol and formaldehyde, wherein catalyst A is made up of by 1: 1: 1 weight ratio ZnO, NaOH and KOH, and catalyst B is by Al
2(SO
4)
3, AlCl
3And FeCl
3Form by 1: 1: 1 weight ratio, catalyst C is by Ti (OC
4H
9)
4, ethyl orthosilicate and borate form by 2: 1: 1 weight ratio.
The specific embodiment two: present embodiment and the specific embodiment one are different is that the consumption of catalyst A is 2.2～2.8 weight portions.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment and the specific embodiment one are different is that the consumption of catalyst A is 2.5 weight portions.Other is identical with the specific embodiment one.
The specific embodiment four: present embodiment and the specific embodiment one are different is that the consumption of catalyst B is 12～14 weight portions.Other is identical with the specific embodiment one.
The specific embodiment five: present embodiment and the specific embodiment one are different is that the consumption of catalyst B is 13 weight portions.Other is identical with the specific embodiment one.
The specific embodiment six: present embodiment and the specific embodiment one are different is that the consumption of catalyst C is 10.5～11.5 weight portions.Other is identical with the specific embodiment one.
The specific embodiment seven: present embodiment and the specific embodiment one are different is that the consumption of catalyst C is 11 weight portions.Other is identical with the specific embodiment one.
The specific embodiment eight: present embodiment and the specific embodiment one are different is that the weight percent concentration of fire resistant pnenolic aldehyde type fiber finish is 80%.Other is identical with the specific embodiment one.
The specific embodiment nine: the preparation method of present embodiment fire resistant pnenolic aldehyde type fiber finish is realized by following reaction: one, get 100～110 weight portion phenol and 115～135 parts by weight of formaldehyde and add reactor, the catalyst A that in reactor, adds 2～3 weight portions again, catalyst A is made up of by 1: 1: 1 weight ratio ZnO, NaOH and KOH, reacts 4h then under 80～100 ℃ of conditions; Two, the catalyst B that adds 10～15 weight portions in reaction vessel again, catalyst B are by Al
2(SO
4)
3, AlCl
3And FeCl
3Form by 1: 1: 1 weight ratio, under 100 ℃ of conditions, react 1～2h then; Three, the catalyst C that adds 10～12 weight portions in reactor again, catalyst C are by Ti (OC
4H
9)
4, ethyl orthosilicate and borate form by 2: 1: 1 weight ratio, treat to carry out decompression distillation after catalyst C dissolves fully; When reaction system is decompressed to 120 ℃, stop decompression distillation, add ethyl acetate solvent simultaneously and be mixed with the ethyl acetate solution that weight percent concentration is 70～80% phenolic resins; Promptly obtain fire resistant pnenolic aldehyde type fiber finish.
Fire resistant pnenolic aldehyde type fiber finish viscosity of the present invention is 200～300mPas.
The specific embodiment ten: present embodiment and the specific embodiment nine are different is that the consumption of catalyst A in step 1 is 2.2～2.8 weight portions.Other reactions steps is identical with the specific embodiment nine.
The specific embodiment 11: present embodiment and the specific embodiment nine are different is that the consumption of catalyst A in step 1 is 2.5 weight portions.Other reactions steps is identical with the specific embodiment nine.
The specific embodiment 12: present embodiment and the specific embodiment nine are different is that the consumption of catalyst B in step 2 is 12～14 weight portions.Other reactions steps is identical with the specific embodiment nine.
The specific embodiment 13: present embodiment and the specific embodiment nine are different is that the consumption of catalyst B in step 2 is 13 weight portions.Other reactions steps is identical with the specific embodiment nine.
The specific embodiment 14: present embodiment and the specific embodiment nine are different is that the consumption of catalyst C in step 3 is 10.5～11.5 weight portions.Other reactions steps is identical with the specific embodiment nine.
The specific embodiment 15: present embodiment and the specific embodiment nine are different is that the consumption of catalyst C in step 3 is 11 weight portions.Other reactions steps is identical with the specific embodiment nine.
The specific embodiment 16: present embodiment and the specific embodiment nine are different is that the weight percent concentration that makes fire resistant pnenolic aldehyde type fiber finish in step 3 is 80%.Other is identical with the specific embodiment nine.
The specific embodiment 17: the preparation method of present embodiment fire resistant pnenolic aldehyde type fiber finish is realized by following reaction: one, get 105 weight portion phenol and 120 parts by weight of formaldehyde and add reactor, the catalyst A that in reactor, adds 2.5 weight portions again, catalyst A is made up of by 1: 1: 1 weight ratio ZnO, NaOH and KOH, reacts 4h then under 90 ℃ of conditions; Two, the catalyst B that adds 13 weight portions in reaction vessel again, catalyst B are by Al
2(SO
4)
3, AlCl
3And FeCl
3Form by 1: 1: 1 weight ratio, under 100 ℃ of conditions, react 2h then; Three, the catalyst C that adds 11 weight portions in reactor again, catalyst C are by Ti (OC
4H
9)
4, ethyl orthosilicate and borate form by 2: 1: 1 weight ratio, treat to carry out decompression distillation after catalyst C dissolves fully; When reaction system is decompressed to 120 ℃, stop decompression distillation, add ethyl acetate solvent simultaneously and be mixed with the ethyl acetate solution that weight percent concentration is 80% phenolic resins; Promptly obtain fire resistant pnenolic aldehyde type fiber finish.
The viscosity of fire resistant pnenolic aldehyde type fiber finish is 250mPas in the present embodiment.
Earlier with fiber impregnation in fire resistant pnenolic aldehyde type fiber finish, 180 ℃ solidify 1h then, be impregnated into again in poly-aryl ethane (PAA) and the modified resin thereof, or with finishing agent with more parallel the arranging of impregnation of fibers put into specific mould and solidified after poly-aryl ethane (PAA) and modified resin thereof mix; Obtain composite, then its performance detected:
1. the mensuration of interlaminar shear strength
Behind 500 ℃ of processing 10min, the interlaminar shear strength of composite has improved (referring to table 1) more than 50%.
Table 1
| 25℃/MPa | 500℃/MPa | |
| Before using finishing agent | 17.8 | 10.2 |
| After using finishing agent | 27.2 | 12.7 |
| On average raising rate of intensity | 53.9％ | 24.5％ |
2. the mensuration of other mechanical properties
The data such as the table 2 of the each side mechanical property of composite:
Table 2
| Compressive strength | The compression amount of touching | TENSILE STRENGTH | Stretch modulus | |
| Before using finishing agent | 120MPa | 13.2GPa | 284MPa | 17.2GPa |
| After using finishing agent | 160MPa | 17.1GPa | 384MPa | 19.3GPa |
| Average raising rate | 33.3％ | 29.5％ | 35.2％ | 12.2％ |
By the data in the table 2 as can be seen, use after the finishing agent, performance of composites has obtained comprehensive lifting, and as seen, this finishing agent is effective to the interface processing of these fibre reinforced composites.
3. the mensuration of electrical property
The data such as the table 3 of the each side electrical property of composite:
Table 3
| Dielectric constant | Dielectric loss angle tangent | |
| Before using finishing agent | 3.14 | 0.00984 |
| After using finishing agent | 2.98 | 0.00978 |
As can be seen from Table 3, the dielectric properties of resulting composite improve behind the use finishing agent processing fiber, and this is that Practical significance is arranged very much to a lot of electronics and electrician's goods.
Claims (10)
1, a kind of fire resistant pnenolic aldehyde type fiber finish, it is characterized in that fire resistant pnenolic aldehyde type fiber finish is to add ethyl acetate solvent in 100～110 weight portion phenol and the reacted product of 115～135 parts by weight of formaldehyde to be mixed with weight percent concentration be that the ethyl acetate solution of 70～80% phenolic resins forms, used the catalyst A of 2～3 weight portions in the reaction of phenol and formaldehyde, the catalyst C of the catalyst B of 10～15 weight portions and 10～12 weight portions, wherein catalyst A is by ZnO, NaOH and KOH form by 1: 1: 1 weight ratio, and catalyst B is by Al
2(SO
4)
3, AlCl
3And FeCl
3Form by 1: 1: 1 weight ratio, catalyst C is by Ti (OC
4H
9)
4, ethyl orthosilicate and borate form by 2: 1: 1 weight ratio.
2, a kind of fire resistant pnenolic aldehyde type fiber finish according to claim 1, the consumption that it is characterized in that catalyst A is 2.2～2.8 weight portions.
3, a kind of fire resistant pnenolic aldehyde type fiber finish according to claim 1, the consumption that it is characterized in that catalyst B is 12～14 weight portions.
4, a kind of fire resistant pnenolic aldehyde type fiber finish according to claim 1, the consumption that it is characterized in that catalyst C is 10.5～11.5 weight portions.
5, the method for preparing the described fire resistant pnenolic aldehyde type fiber finish of claim 1, the preparation method who it is characterized in that fire resistant pnenolic aldehyde type fiber finish is realized by following reaction: one, get 100～110 weight portion phenol and 115～135 parts by weight of formaldehyde and add reactor, the catalyst A that in reactor, adds 2～3 weight portions again, catalyst A is made up of by 1: 1: 1 weight ratio ZnO, NaOH and KOH, reacts 4h then under 80～100 ℃ of conditions; Two, the catalyst B that adds 10～15 weight portions in reaction vessel again, catalyst B are by Al
2(SO
4)
3, AlCl
3And FeCl
3Form by 1: 1: 1 weight ratio, under 100 ℃ of conditions, react 1～2h then; Three, the catalyst C that adds 10～12 weight portions in reactor again, catalyst C are by Ti (OC
4H
9)
4, ethyl orthosilicate and borate form by 2: 1: 1 weight ratio, treat to carry out decompression distillation after catalyst C dissolves fully; When reaction system is decompressed to 120 ℃, stop decompression distillation, add ethyl acetate solvent simultaneously and be mixed with the ethyl acetate solution that weight percent concentration is 70～80% phenolic resins; Promptly obtain fire resistant pnenolic aldehyde type fiber finish.
6, the preparation method of fire resistant pnenolic aldehyde type fiber finish according to claim 5, the consumption that it is characterized in that catalyst A in step 1 is 2.2～2.8 weight portions.
7, the preparation method of fire resistant pnenolic aldehyde type fiber finish according to claim 5, the consumption that it is characterized in that catalyst A in step 1 is 2.5 weight portions.
8, the preparation method of fire resistant pnenolic aldehyde type fiber finish according to claim 5, the consumption that it is characterized in that catalyst B in step 2 is 12～14 weight portions.
9, the preparation method of fire resistant pnenolic aldehyde type fiber finish according to claim 5, the consumption that it is characterized in that catalyst B in step 2 is 13 weight portions.
10, the preparation method of fire resistant pnenolic aldehyde type fiber finish according to claim 5, the consumption that it is characterized in that catalyst C in step 3 is 10.5～11.5 weight portions.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101448975A CN100552126C (en) | 2007-12-21 | 2007-12-21 | A kind of fire resistant pnenolic aldehyde type fiber finish and preparation method thereof |
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|---|---|---|---|
| CNB2007101448975A CN100552126C (en) | 2007-12-21 | 2007-12-21 | A kind of fire resistant pnenolic aldehyde type fiber finish and preparation method thereof |
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|---|---|
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| CN100552126C true CN100552126C (en) | 2009-10-21 |
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| CN104817821B (en) * | 2015-04-10 | 2016-09-21 | 航天材料及工艺研究所 | A kind of SiO2-TiO2inorganic hybridization thermosetting phenolic resin and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| 常温固化耐高温酚醛树脂胶粘剂的研制. 庞金兴等.武汉工业大学学报，第22卷第3期. 2000 |
| 常温固化耐高温酚醛树脂胶粘剂的研制. 庞金兴等.武汉工业大学学报，第22卷第3期. 2000 * |
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Granted publication date: 20091021 Termination date: 20101221 |