CN106867007A - A kind of preparation method of resin impregnating glass fiber compound material - Google Patents
A kind of preparation method of resin impregnating glass fiber compound material Download PDFInfo
- Publication number
- CN106867007A CN106867007A CN201710145358.7A CN201710145358A CN106867007A CN 106867007 A CN106867007 A CN 106867007A CN 201710145358 A CN201710145358 A CN 201710145358A CN 106867007 A CN106867007 A CN 106867007A
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- China
- Prior art keywords
- glass fibre
- preparation
- phenolic resin
- compound material
- glass fiber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08K3/38—Boron-containing compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
A kind of major design of the present invention method of production of resin impregnating glass fiber compound material.Specifically：Glass fibre is surface-treated using the method for heat treatment+acid etch+coupling agent treatment；Then by the boron modified phenolic resin alcoholic solution of glass fibre immersion certain mass concentration zirconium boride, curing molding in Muffle furnace is put into after vacuum impregnation, the first product for obtaining is put into the phenolic resin alcoholic solution of certain mass concentration, repeated impregnations solidification obtains finished product.Preparation technology is optimized by a series of performance characterization, finally gives the resin impregnating glass fiber compound material of required density.It is an advantage of the invention that：Density as little as 0.25~0.4g/cm3, with preferably antioxygenic property, and process is simple, can be used for high-temperature hot protection field.
Description
Technical field
The invention belongs to high temperature heat-resistant protective materials field, it is related to a kind of low-density resin impregnating glass fibre to be combined
The preparation method of material.
Background technology
Spacecraft returns to terrestrial time, can enter atmosphere with the speed of a superelevation, and kinetic energy is converted into heat energy, by shock wave spoke
Heat is penetrated and spread, spacecraft surface temperature is drastically raised.Spacecraft needs to bear thousands of degrees Celsius of height during reentering
Temperature.To ensure the smooth return of spacecraft, it is necessary to take effective thermal protection measure.
The carbonization type lightweight thermally protective materials of research at present are general with phenolic resin as matrix, and its is with low cost, heat resistance
Can be good with flushing resistance, with prominent instantaneous resistance to elevated temperatures.But the resin impregnating material of matrix is done with it
Density it is higher, such as phenolic aldehyde-quartz composite averag density be 0.55g/cm3.This density cannot meet modern space flight
To low-density, high performance requirement, resin impregnating glass fiber compound material density involved in the present invention is low, energy in field
Enough for aircraft thermal protection provides light composite material.
The content of the invention
Problem to be solved by this invention is：It is big for phenolic resin composite density, hot environment is easily oxidized etc.
Problem, proposes a kind of method for reducing phenolic resin composite density, strengthening heat resistance.
Design philosophy of the invention is the bond effect for increasing glass fibre and phenolic resin by being surface-treated, by boron
Change zirconium coating enhancing antioxygenic property.The fiberglass surfacing of commercialization typically has one layer of sizing material being made up of composite components,
With the effect such as friction resistant, anti-aging, but it is bonding with fiber surface to be detrimental to resin, the present invention by being heat-treated+it is harsh
Erosion+coupling agent treatment, aoxidizes surface size, and increases the cohesive force of glass fibre and resin, improves the interface of composite
Performance.Thermal protective performance and the stable oxidation product film of mechanical performance are formed under zirconium boride high temperature, it possesses solid-liquid two-phase.
Solid phase forms skeleton, and liquid phase closing composite material surface stomata prevents the flowing of gas and then prevents further oxidation, improves anti-
Oxidation susceptibility.
The step of present invention surface treatment, is as follows：(1) the original of fiberglass surfacing is made using high temperature using heat treatment
Sizing material oxidation Decomposition；(2) oxide etch treatment is carried out to glass fibre using certain density watery hydrochloric acid；(3) certain matter is utilized
Measure the silane coupler KH-560 treatment of fraction.
The present invention provides the preparation method of resin impregnating glass fiber material, and its preparation method has following steps：
(1) glass fibre 3 D weaving body is surface-treated；
(2) a certain amount of zirconium boride is added in the boron modified phenolic resin alcoholic solution of certain mass concentration, then
Surface treated glass fibre 3 D weaving body immerses the solution, submerges the 1/2 of volume, using vacuum impregnation technique, system
Obtain half preform；
(3) obtained half preform is put into curing molding in Muffle furnace, first product is obtained；
(4) first product is not impregnated with the boron modified phenolic resin alcoholic solution of part immersion certain mass concentration, using vacuum
Dipping, curing mode, the resin impregnating glass fiber compound material finished product of density needed for being obtained.
Obtained composite density as little as 0.25~0.4g/cm3 of the invention, with preferable antioxygenic property, is applicable
In refractory surfaces thermal protection field.
Brief description of the drawings
Accompanying drawing is preparation technology flow chart of the present invention
Specific embodiment
Raw material glass fibre three-dimensional knitted body is pre-processed first, is comprised the following steps that：
(1) it is heat-treated：Glass fibre 3 D weaving body is put into Muffle furnace, treatment temperature is 350 DEG C, process time is
30 minutes；Then by through the glass fibre of Overheating Treatment, ultrasound is cleared up 40 minutes in suds, and cleaned with distilled water, completely
The sizing material oxide of removal glass fibre after heat treatment remained on surface；It is finally putting into 80 DEG C of drying in air dry oven.
(2) acid etch treatment：Glass fibre 3 D weaving body is put into the watery hydrochloric acid that mass fraction is 20%, at normal temperature
Reason, process time is 4 hours；Then the glass fibre that will be processed by acid etch ultrasound cleaning 40 minutes in suds, and
Cleaned with distilled water；It is finally putting into 80 DEG C of drying in air dry oven.
(3) coupling agent treatment：Glass fibre 3 D weaving body is put into the KH-560 coupling agent solutions that mass fraction is 3%
In, normal temperature treatment, process time is 30 minutes, is then placed in 80 DEG C of drying in air dry oven.
Then using surface treated glass fibre 3 D weaving body as reinforcement, using vacuum impregnation technique, system
Obtain resin impregnating glass fiber compound material.Comprise the following steps that：
(1) vacuum impregnation：It is 9%, phenolic aldehyde mass fraction that glass fibre 3 D weaving body is put into zirconium boride mass fraction
In 25% solution, to submerge the 1/2 of volume, it is placed in vacuum air dry oven, extracts air in case using vavuum pump until molten
Liquid bubble-free is produced, and maintains vacuum condition, normal temperature dipping 2 hours；
(2) dry：The glass fibre 3 D weaving body for completing will be impregnated to be put into air dry oven, 24 are dried at 80 DEG C small
When.
(3) solidify：Dried glass fibre is put into Muffle furnace, is solidified at 120 DEG C 1 hour, it is then solid at 150 DEG C
Change 3.5 hours, last furnace cooling obtains first product.
(4) first product is not impregnated with the boron modified phenolic resin alcoholic solution of part immersion certain mass concentration, using vacuum
Dipping, curing mode, the resin impregnating glass fiber compound material finished product of density needed for being obtained.
Unless otherwise stated, the number range that this patent is related to is included between end value and endpoints thereof (i.e. upper and lower boundary)
Arbitrary value.
By way of example, the present invention will be further described, for explaining main innovation point of the invention, but implements
Mode must not be used to explain limiting the scope of the invention.
Claims (4)
1. a kind of preparation method of resin impregnating glass fiber compound material, it is characterised in that：
(1) glass fibre 3 D weaving body is surface-treated；
(2) a certain amount of zirconium boride is added in the boron modified phenolic resin alcoholic solution of certain mass concentration, then process
The glass fibre 3 D weaving body of surface treatment immerses the solution, submerges the 1/2 of volume, using vacuum impregnation technique, is obtained half
Preform；
(3) obtained half preform is put into curing molding in Muffle furnace, first product is obtained；
(4) by first product be not impregnated with part immersion certain mass concentration boron modified phenolic resin alcoholic solution in, using vacuum impregnation,
Curing mode, the resin impregnating glass fiber compound material finished product of density needed for being obtained.
2. preparation method according to claim 1, it is characterised in that using the side of heat treatment+acid etch+coupling agent treatment
Method is surface-treated to glass fibre, comprises the following steps：(1) glass fibre is made using 350 DEG C of high temperature using heat treatment
Original sizing material oxidation Decomposition on surface；(2) using the watery hydrochloric acid that mass fraction is 15~20% is carried out to glass fibre oxidation quarter
Erosion is processed；(3) using the silane coupler KH-560 treatment that mass fraction is 2~3%.
3. preparation method according to claim 1, it is characterised in that the described boron modified phenolic resin alcohol containing zirconium boride
In solution, the mass fraction of zirconium boride is 7%~11%, and the mass fraction of phenolic resin is 15%~25%.
4. preparation method according to claim 1, it is characterised in that described curing molding mode is：First it is warming up to 120
DEG C, kept for 1 hour, 150 DEG C are then warming up to again, kept for 3.5 hours, last furnace cooling obtains finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710145358.7A CN106867007A (en) | 2017-03-13 | 2017-03-13 | A kind of preparation method of resin impregnating glass fiber compound material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710145358.7A CN106867007A (en) | 2017-03-13 | 2017-03-13 | A kind of preparation method of resin impregnating glass fiber compound material |
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| Publication Number | Publication Date |
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| CN106867007A true CN106867007A (en) | 2017-06-20 |
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| CN201710145358.7A Pending CN106867007A (en) | 2017-03-13 | 2017-03-13 | A kind of preparation method of resin impregnating glass fiber compound material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880326A (en) * | 2017-11-21 | 2018-04-06 | 常州可赛成功塑胶材料有限公司 | A kind of Wear-resistant sole material |
| CN108948484A (en) * | 2018-06-06 | 2018-12-07 | 安徽师范大学 | A kind of preparation method of high molecular based PTC heating tape |
| CN112936657A (en) * | 2021-01-29 | 2021-06-11 | 哈尔滨工业大学 | Method for reinforcing phenolic resin composite material by using fiber braid with antioxidant laminated structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224688A (en) * | 2013-04-16 | 2013-07-31 | 中国兵器工业集团第五三研究所 | Ablation resistant composite material |
| CN105111748A (en) * | 2015-07-31 | 2015-12-02 | 沈阳理工大学 | Hot vulcanized silicone rubber/boron phenol-formaldehyde resin based erosion-resisting material and preparation method therefor |
-
2017
- 2017-03-13 CN CN201710145358.7A patent/CN106867007A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224688A (en) * | 2013-04-16 | 2013-07-31 | 中国兵器工业集团第五三研究所 | Ablation resistant composite material |
| CN105111748A (en) * | 2015-07-31 | 2015-12-02 | 沈阳理工大学 | Hot vulcanized silicone rubber/boron phenol-formaldehyde resin based erosion-resisting material and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 王爽等: ""表面处理对硼／酚醛复合材料力学性能的影响"", 《第16届北方七省市区力学学会学术会议 力学与工程应用（第十六卷）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880326A (en) * | 2017-11-21 | 2018-04-06 | 常州可赛成功塑胶材料有限公司 | A kind of Wear-resistant sole material |
| CN108948484A (en) * | 2018-06-06 | 2018-12-07 | 安徽师范大学 | A kind of preparation method of high molecular based PTC heating tape |
| CN112936657A (en) * | 2021-01-29 | 2021-06-11 | 哈尔滨工业大学 | Method for reinforcing phenolic resin composite material by using fiber braid with antioxidant laminated structure |
| CN112936657B (en) * | 2021-01-29 | 2023-01-31 | 哈尔滨工业大学 | Method for reinforcing phenolic resin composite material by using fiber braid with anti-oxidation laminated structure |
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Application publication date: 20170620 |