CN101195966A - Fire resistant pnenolic aldehyde type fiber finish and method for producing the same - Google Patents
Fire resistant pnenolic aldehyde type fiber finish and method for producing the same Download PDFInfo
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- CN101195966A CN101195966A CNA2007101448975A CN200710144897A CN101195966A CN 101195966 A CN101195966 A CN 101195966A CN A2007101448975 A CNA2007101448975 A CN A2007101448975A CN 200710144897 A CN200710144897 A CN 200710144897A CN 101195966 A CN101195966 A CN 101195966A
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Abstract
The invention belongs to high temperature resistant phenolic aldehyde type fiber finishing agent and the preparation method thereof, which relates to fiber finishing agent and the preparation method thereof. The invention solves the problems that the interface combination of the present quartz fiber reinforced polyarylacetylene (PAA) and the high-performance resin matrix composite with aromatic heterocycles of other main chains is poor, and the air bubble is generated at the high temperature, etc. The product of the invention is formed by adding ethyl acetate solvent to dispense the solution after the reaction of phenyl hydrate and formaldehyde, and the preparation method has the following steps that firstly, the phenyl hydrate and the formaldehyde are taken to be added into catalyzer A, and reacts for 4 hours under the condition of 80 to 100 DEG C; secondly, catalyzer B is added, and reacts for one to two hours under the condition of 100 DEG C; thirdly, catalyzer C is added, and the pressure is reduced and the catalyzer C is distilled after being completely dissolved; the ethyl acetate is added to dispense the solution. The processed high-performance composite material of the product of the invention can be used under the high temperature condition of 450 to 500 DEG C, and the phenomenon of the high temperature bubbling is eliminated. Compared with the non-processed composite material through the finishing agent of the invention, the shearing strength between normal temperature layers after being processed through the product of the invention is increased by more than 50 percent.
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. 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, 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.
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 a kind 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 a kind 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 a kind 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 a kind 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 a kind 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.
Priority Applications (1)
| 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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| 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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| Publication Number | Publication Date |
|---|---|
| CN101195966A true CN101195966A (en) | 2008-06-11 |
| CN100552126C CN100552126C (en) | 2009-10-21 |
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|---|---|---|---|
| CNB2007101448975A Expired - Fee Related 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817821A (en) * | 2015-04-10 | 2015-08-05 | 航天材料及工艺研究所 | SiO2-TiO2 inorganic hybrid thermosetting thermosetting phenolic resin and preparation method thereof |
-
2007
- 2007-12-21 CN CNB2007101448975A patent/CN100552126C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817821A (en) * | 2015-04-10 | 2015-08-05 | 航天材料及工艺研究所 | SiO2-TiO2 inorganic hybrid thermosetting thermosetting phenolic resin and preparation method thereof |
| 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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| Publication number | Publication date |
|---|---|
| CN100552126C (en) | 2009-10-21 |
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Granted publication date: 20091021 Termination date: 20101221 |