CN106082709A - Automotive natural gas bottle glass fibre dedicated film-forming agent and preparation method thereof - Google Patents
Automotive natural gas bottle glass fibre dedicated film-forming agent and preparation method thereof Download PDFInfo
- Publication number
- CN106082709A CN106082709A CN201610401779.7A CN201610401779A CN106082709A CN 106082709 A CN106082709 A CN 106082709A CN 201610401779 A CN201610401779 A CN 201610401779A CN 106082709 A CN106082709 A CN 106082709A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- type epoxy
- bisphenol
- glass fibre
- natural gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/36—Epoxy resins
Abstract
The invention discloses a kind of automotive natural gas bottle glass fibre dedicated film-forming agent and preparation method thereof, it is made up of the component of following weight percentage ratio: the bisphenol A type epoxy resin of 30%～70%, the bisphenol A type epoxy resin polyethylene glycol oxide graft copolymer of 6%～10%, the ethylene oxide propylene oxide block copolymer of 0.1%～10%, surplus is deionized water.The bisphenol A type epoxy resin polyethylene glycol oxide graft copolymer that the present invention uses and bisphenol A type epoxy resin have preferable intermiscibility, and when being applied to glass fibre as film former, in the later process course of processing, the epoxy radicals at two ends may also participate in curing reaction, thus improves the mechanical property of material.The glass fibre wetting-out rate using the film former of the present invention to prepare is fast, mechanical property good, and the glass fibre reinforced plastic pressure gas container made disclosure satisfy that automotive natural gas bottle indices requirement.
Description
Technical field
The present invention relates to a kind of film former and preparation method thereof, be specifically related to a kind of automotive natural gas bottle glass fibre special
With film former and preparation method thereof.
Background technology
Automobile with compressed natural gas is the vehicle using compressed natural gas (being called for short CNG) as motor vehicle fuel, from the point of view of in-use automotive,
Sizing gasoline car is reequiped, in the case of retaining former car oil supply system, increases a set of special compressed natural gas device, form pressure
Contracting gas-fueled vehicles, the conversion of fuel only needs toggle switch.Add and fill natural gas wheeled 200 km, be particularly suitable for
Bus, city taxi, round-trip distance minibus, the car in face and other vehicle of unit less than 200 kilometers.
Compared with using gasoline, compressed natural gas has that safety is higher, fuel knock performance more preferably, save fuel cost
With, reduce cost of transportation, extend maintenance cycle and the more advantage such as environmental protection.
Along with development and the development of glass fibre reinforced plastics technology of gas vehicle technology, automotive natural gas bottle is transitioned into fiberglass by steel cylinder
Gas cylinder, its performance have also been obtained and significantly promotes.
Compared with traditional steel cylinder, glass fibre reinforced plastic pressure gas container has the advantages such as specific strength is high, damping property is good, fail-safety is good.
Summary of the invention
It is an object of the invention to solve the problems referred to above, it is provided that a kind of automotive natural gas bottle glass fibre dedicated film-forming agent
And preparation method thereof.
The technical scheme realizing above-mentioned purpose of the present invention is: a kind of automotive natural gas bottle glass fibre dedicated film-forming agent,
It is made up of the component of following weight percentage ratio: the bisphenol A type epoxy resin of 30%～70%, the bisphenol type epoxy of 6%～10%
Resin-polyethylene oxide graft copolymer, the ethylene oxide-propylene oxide block copolymer of 0.1%～10%, surplus is deionization
Water.
Preferably be made up of the component of following weight percentage ratio: the bisphenol A type epoxy resin of 40%～65%, 6.5%～9% double
Phenol A type epoxy resin-polyethylene glycol oxide graft copolymer, the ethylene oxide-propylene oxide block copolymer of 1%～5%, surplus is
Deionized water.
More preferably be made up of the component of following weight percentage ratio: the bisphenol A type epoxy resin of 50%～60%, 7%～8% double
Phenol A type epoxy resin-polyethylene glycol oxide graft copolymer, the ethylene oxide-propylene oxide block copolymer of 2%～4%, surplus is
Deionized water.
Wherein, the consumption of bisphenol A type epoxy resin-polyethylene glycol oxide graft copolymer is most important, when its consumption is less than
When 6%, obtained film former granule is relatively big, and the glass fibre wetting-out rate made is relatively slow, and mechanical property is poor, thus can not
Make qualified automotive natural gas bottle；And when its consumption is higher than 10%, not only increases production cost, and can affect equally
Glass fibre correlated performance.
The epoxide equivalent of above-mentioned bisphenol A type epoxy resin is 185～206, preferably 196.
The preparation method of above-mentioned automotive natural gas bottle glass fibre dedicated film-forming agent has steps of:
1. bisphenol A type epoxy resin is heated to 70～80 DEG C；2. by ethylene oxide-propylene oxide block copolymer, bisphenol A-type
Bisphenol A type epoxy resin after 1. epoxy resin-polyethylene glycol oxide graft copolymer and step heat joins according to proportioning
In emulsifying kettle, stir at a temperature of 60～70 DEG C；3. stirring motor is opened, the stirring of 1000～1500 revs/min
Being slowly added to deionized water under speed, after being aqueous to mass transfer, continuing to be diluted with water to emulsion solid content is 50 ± 1.0%.
Above-mentioned bisphenol A type epoxy resin-polyethylene glycol oxide graft copolymer is under Louis acid catalysis, makes bisphenol A-type
Epoxy resin and polyethylene glycol oxide carry out graft reaction and prepare.The epoxide equivalent of bisphenol A type epoxy resin used be 185～
206, preferably 196；The molecular weight of described polyethylene glycol oxide is 100000～1000000, preferably 300000～700000, more
It is preferably 500000～550000；Described lewis acid is aluminum chloride, iron chloride, boron trifluoride or fluoroform sulphonate, excellent
Elect aluminum chloride or iron chloride as.
Make wetting agent with silane coupler, non-ionic lubricant, softening agent etc. when the film former of the present invention is applied, become
The usage amount of membrane is 5～8wt%(to occupy more than the 65% of effective constituent).
The good effect that the present invention has: the bisphenol A type epoxy resin that (1) present invention uses-polyethylene glycol oxide grafting is altogether
The centre of polymers is polyether segment, and two ends are epoxy radicals, and it not only has preferable intermiscibility with bisphenol A type epoxy resin, and
And when being applied to glass fibre as film former, in the later process course of processing, the epoxy radicals at two ends may also participate in solidification
Reaction, thus improve the mechanical property of material.The glass fibre wetting-out rate (2) using the film former of the present invention to prepare is fast,
Mechanical property is good, and the glass fibre reinforced plastic pressure gas container made disclosure satisfy that automotive natural gas bottle indices requirement.
Detailed description of the invention
(embodiment 1)
The automotive natural gas bottle glass fibre dedicated film-forming agent of the present embodiment is made up of the component of following weight percentage ratio:
The bisphenol A type epoxy resin (trade mark is E51, and its epoxide equivalent is 196) of 53.7%, the bisphenol A type epoxy resin-polyoxy of 7.3%
Change grafted ethylene copolymer, the ethylene oxide-propylene oxide block copolymer of 3%, 36% deionized water.
The preparation method of this automotive natural gas bottle glass fibre dedicated film-forming agent has steps of:
1. bisphenol A type epoxy resin is heated to 75 DEG C.
2. by ethylene oxide-propylene oxide block copolymer, bisphenol A type epoxy resin-polyethylene glycol oxide graft copolymer
And step 1. heat after bisphenol A type epoxy resin join in emulsifying kettle according to proportioning, at a temperature of 65 DEG C, stirring is all
Even.
Above-mentioned bisphenol A type epoxy resin-polyethylene glycol oxide graft copolymer is that (the present embodiment is chlorination at lewis acid
Aluminum) catalysis under, (molecular weight is with polyethylene glycol oxide to make bisphenol A type epoxy resin (trade mark is E51, and its epoxide equivalent is 196)
500000～550000) carry out graft reaction to prepare.
3. open stirring motor, under the mixing speed of 1200 revs/min, be slowly added to deionized water, to mass transfer be
After aqueous, continuing to be diluted with water to emulsion solid content is 50 ± 1.0%.
The granularity of the automotive natural gas bottle glass fibre dedicated film-forming agent that the present embodiment prepares is 0.47 micron, dilute to it
Release stability and dewatering ability is tested, the results are shown in Table 2.
The method of testing of dilution stability is: solid content is diluted to 5% placement 24h.
The method of testing of dewatering ability is: 4000 revs/min of 10mL test tube, 30min.
(embodiment 2～embodiment 3)
The film former of each embodiment is substantially the same manner as Example 1, and difference is shown in Table 1.
The granularity of the film former of each embodiment, dilution stability and dewatering ability test result are still shown in Table 2.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Bisphenol A type epoxy resin | 53.7% | 50% | 60% | 53.7% |
| Emulsifying agent A | 7.3% | 7% | 8% | 5.7% |
| Emulsifying agent B | 3% | 2% | 4% | 3% |
| Deionized water | 36% | 41% | 28% | 37.6% |
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Granularity | 0.47 micron | 0.49 micron | 0.38 micron | 0.72 micron |
| Dilution stability | 5% upper strata 4.94,5% lower floor 5.13, difference 0.19 | 5% upper strata 4.77,5% lower floor 4.95, difference 0.18 | 5% upper strata 4.85,5% lower floor 5.07, difference 0.22 | 5% upper strata 4.92,5% lower floor 5.05, difference 0.13 |
| Dewatering ability | Upper strata 0.5mL clear water | Upper strata 0.5mL clear water | Upper strata 0.5mL clear water | Upper strata 0.5mL clear water |
(comparative example 1)
The film former of comparative example 1 is substantially the same manner as Example 1, and difference is still shown in Table 1.
The granularity of the film former of comparative example 1, dilution stability and dewatering ability test result are still shown in Table 2.
(application examples 1)
The film former of embodiment 1 is used in glass fiber yarn drawing process, the nol ring shear strength etc. of test yarn, with
Time be all referred to as Hansen film former with the film former of comparative example 1 and Hansen film former below Epikote 3510-W-60A() enter
Row contrast, the results are shown in Table 3.
Table 3
| Embodiment 1 | Comparative example 1 | Hansen film former | |
| Shear strength/MPa | 47.31 | 45.26 | 42.48 |
| The coefficient of variation/% | 2.26 | 4.72 | 6.73 |
| Fiber content % | 76.63 | 75.58 | 77.54 |
As can be seen from Table 3: use embodiment 1 film former draw yarn there is higher shear strength, compared to
Hansen film former improves more than 10%.
(application examples 2)
Respectively the film former of embodiment 1, the film former of comparative example 1 and Hansen film former are used for the preparation of fiberglass products
In, and tested glass fibre correlated performance, the results are shown in Table 4.
Table 4
| Correlated performance | Embodiment 1 | Comparative example 1 | Hansen film former | Standard |
| Line density (tex) | 2389 | 1914 | 2416 | 2300～2500 |
| Moisture content (%) | 0.08 | 0.14 | 0.09 | It is not more than 0.2 |
| Combustible content (%) | 0.52 | 0.62 | 0.50 | 0.35～0.65 |
| Strongly (N/tex) | 0.56 | 0.27 | 0.48 | Not less than 0.35 |
| Impregnability (second) | 22 | 43 | 28 | It is not more than 35 |
As can be seen from Table 4: the fiberglass products correlated performance that the film former of embodiment 1 and Hansen film former prepare is equal
Conformance with standard, hence it is evident that be better than the film former of comparative example 1.
(application examples 3)
Respectively the film former of embodiment 1, the film former of comparative example 1 and Hansen film former are used for the preparation of glass fibre reinforced plastic pressure gas container
In, circulation of qi promoting bottle bottle test (standard No. GB24162-2009) of going forward side by side, the results are shown in Table 5.
Table 5
| Embodiment 1 | Comparative example 1 | Hansen film former | |
| Workability | Qualified | Qualified | Qualified |
| Air-tightness | Qualified | Defective | Qualified |
| Crushing resistance | Qualified | Qualified | Defective |
| Impact resistance | Qualified | Defective | Defective |
| Be full of cracks number | 0 | 4 | 3 |
| Ultrasound injury detects | 0 | 3 | 5 |
As can be seen from Table 5: the glass fibre reinforced plastic pressure gas container using the film former of embodiment 1 to prepare is fully able to meet automobile-used natural
The requirement of gas cylinder.
Claims (8)
1. an automotive natural gas bottle glass fibre dedicated film-forming agent, it is characterised in that by the component system of following weight percentage ratio
Become: the bisphenol A type epoxy resin of 30%～70%, the bisphenol A type epoxy resin of 6%～10%-polyethylene glycol oxide graft copolymer,
The ethylene oxide-propylene oxide block copolymer of 0.1%～10%, surplus is deionized water.
Automotive natural gas bottle glass fibre dedicated film-forming agent the most according to claim 1, it is characterised in that by following heavy
The component of amount percentage ratio is made: the bisphenol A type epoxy resin of 40%～65%, the bisphenol A type epoxy resin-polyoxygenated of 6.5%～9%
Grafted ethylene copolymer, the ethylene oxide-propylene oxide block copolymer of 1%～5%, surplus is deionized water.
Automotive natural gas bottle glass fibre dedicated film-forming agent the most according to claim 2, it is characterised in that by following heavy
The component of amount percentage ratio is made: the bisphenol A type epoxy resin of 50%～60%, the bisphenol A type epoxy resin-polyoxyethylene of 7%～8%
Alkene graft copolymer, the ethylene oxide-propylene oxide block copolymer of 2%～4%, surplus is deionized water.
4. according to the glass fibre dedicated film-forming agent of the automotive natural gas bottle one of claims 1 to 3 Suo Shu, it is characterised in that:
The epoxide equivalent of described bisphenol A type epoxy resin is 185～206.
Automotive natural gas bottle glass fibre dedicated film-forming agent the most according to claim 4, it is characterised in that: described bis-phenol
The epoxide equivalent of A type epoxy resin is 196.
6. the automotive natural gas bottle preparation method of glass fibre dedicated film-forming agent that one of claims 1 to 3 is described, its feature
It is to have steps of:
1. bisphenol A type epoxy resin is heated to 70～80 DEG C；
2. by ethylene oxide-propylene oxide block copolymer, bisphenol A type epoxy resin-polyethylene glycol oxide graft copolymer and
Bisphenol A type epoxy resin after 1. step heats joins in emulsifying kettle according to proportioning, and at a temperature of 60～70 DEG C, stirring is all
Even；
3. open stirring motor, under the mixing speed of 1000～1500 revs/min, be slowly added to deionized water, to mass transfer
After aqueous, continuing to be diluted with water to emulsion solid content is 50 ± 1.0%.
The preparation method of automotive natural gas bottle glass fibre dedicated film-forming agent the most according to claim 6, its feature exists
In: the epoxide equivalent of described bisphenol A type epoxy resin is 185～206.
The preparation method of automotive natural gas bottle glass fibre dedicated film-forming agent the most according to claim 7, its feature exists
In: the epoxide equivalent of described bisphenol A type epoxy resin is 196.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610401779.7A CN106082709A (en) | 2016-06-08 | 2016-06-08 | Automotive natural gas bottle glass fibre dedicated film-forming agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610401779.7A CN106082709A (en) | 2016-06-08 | 2016-06-08 | Automotive natural gas bottle glass fibre dedicated film-forming agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106082709A true CN106082709A (en) | 2016-11-09 |
Family
ID=57228111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610401779.7A Pending CN106082709A (en) | 2016-06-08 | 2016-06-08 | Automotive natural gas bottle glass fibre dedicated film-forming agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106082709A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110723912A (en) * | 2019-11-18 | 2020-01-24 | 常州天马集团有限公司（原建材二五三厂） | Preparation method of novel film-forming agent for glass fiber |
| CN115851091A (en) * | 2022-12-01 | 2023-03-28 | 广东新华强玻璃科技有限公司 | Toughened glass with high impact strength and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101553443A (en) * | 2006-02-27 | 2009-10-07 | Ocv智识资本有限责任公司 | Sizing for high performance glass fibers and composite materials incorporating same |
| CN101880967A (en) * | 2010-06-23 | 2010-11-10 | 北京航空航天大学 | Method for preparing self-emulsifying carbon fiber sizing agent component |
| CN102531412A (en) * | 2011-12-25 | 2012-07-04 | 泰山玻璃纤维有限公司 | Special glass fiber film-forming agent for wind turbine blades and preparation method thereof |
-
2016
- 2016-06-08 CN CN201610401779.7A patent/CN106082709A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101553443A (en) * | 2006-02-27 | 2009-10-07 | Ocv智识资本有限责任公司 | Sizing for high performance glass fibers and composite materials incorporating same |
| CN101880967A (en) * | 2010-06-23 | 2010-11-10 | 北京航空航天大学 | Method for preparing self-emulsifying carbon fiber sizing agent component |
| CN102531412A (en) * | 2011-12-25 | 2012-07-04 | 泰山玻璃纤维有限公司 | Special glass fiber film-forming agent for wind turbine blades and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110723912A (en) * | 2019-11-18 | 2020-01-24 | 常州天马集团有限公司（原建材二五三厂） | Preparation method of novel film-forming agent for glass fiber |
| CN115851091A (en) * | 2022-12-01 | 2023-03-28 | 广东新华强玻璃科技有限公司 | Toughened glass with high impact strength and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105062395B (en) | Two component epoxy glue and preparation method thereof | |
| CN107513211A (en) | It is a kind of it is low distribute, low smell automobile using polypropylene composite material | |
| CN103756125B (en) | A kind of PP composite material cross beams of automobile water tank and preparation method | |
| CN102604469A (en) | Latent self-repair microcapsule and preparation method thereof | |
| CN106243699B (en) | Polyamide composite resin composition for fuel filler pipe | |
| CN103772921B (en) | A kind of fiberglass reinforced polyethyleneterephthalate/polycarbonate alloy | |
| CN103059583B (en) | Emulsified asphalt and preparation method thereof | |
| CN103834161A (en) | High-temperature resistant semi aromatic nylon composite material and preparation method thereof | |
| CN106082709A (en) | Automotive natural gas bottle glass fibre dedicated film-forming agent and preparation method thereof | |
| CN103613924A (en) | Anti-electrostatic, reinforced and toughened nylon 612 composite material and preparation method and application thereof | |
| CN102558736A (en) | Polypropylene composite material for automotive instrument panel and preparation method for polypropylene composite material | |
| CN111057369A (en) | Carbon fiber reinforced polyamide composite material pre-soaked basalt fiber cloth and preparation method thereof | |
| CN105733091A (en) | High-fiber-content continuous basalt fiber reinforced flame-retarding PP master batch and application thereof | |
| CN106397932A (en) | Composite for fiber-reinforced plastic inspection chamber and preparation method thereof | |
| CN106810802A (en) | A kind of preparation method for regenerating weather-proof composite engineering plastics | |
| KR20170110915A (en) | Long fiber reinforced polyamide pellet, polyamide resin composition including the same and molded article thereof | |
| CN103980721A (en) | Preparing method of epoxy compound type emulsified asphalt | |
| CN107674414A (en) | A kind of hydrolysis enhancing nylon material and preparation method thereof | |
| CN101157777A (en) | Modified polypropylene resin having good hydrophilicity and preparation method thereof | |
| CN106242319A (en) | A kind of high-performance glass fiber wetting agent | |
| CN112831135A (en) | High-impact-resistance PVC pipe material and preparation method and application thereof | |
| CN104744879A (en) | Recycling and reusing process for phenolic resin composite waste material | |
| CN106188400A (en) | A kind of preparation technology of polystyrene multi-component copolymer macromolecular material | |
| CN107955270B (en) | Polypropylene nano composite material and preparation method thereof | |
| CN114196324A (en) | Water-emulsion type rubber asphalt waterproof coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |
|
| RJ01 | Rejection of invention patent application after publication |