CN103771732B - The treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre - Google Patents
The treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre Download PDFInfo
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- CN103771732B CN103771732B CN201410013132.8A CN201410013132A CN103771732B CN 103771732 B CN103771732 B CN 103771732B CN 201410013132 A CN201410013132 A CN 201410013132A CN 103771732 B CN103771732 B CN 103771732B
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Abstract
The invention discloses the treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre, described treating compound comprises coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and water, the solid masses of described treating compound accounts for 4 ~ 12% for the treatment of compound total mass, and surplus is water; Described coupling agent adopts silane coupling agent; Described lubricant adopts water miscible PEG series lubricant agent; Described membrane-forming agent is the blend of epoxy emulsion, organic siloxane modified epoxy emulsion and polyaminoester emulsion; Described tensio-active agent is the blend of nonionogenic tenside and cats product; Described pH value regulator is acid; The ratio that each component accounts for treating compound solid masses in its solid content is as follows: coupling agent 5 ~ 15%, lubricant 5 ~ 20%, epoxy emulsion 10 ~ 45%, organic siloxane modified epoxy emulsion 10 ~ 50%, polyaminoester emulsion 5 ~ 20%, membrane-forming agent 65 ~ 80%, tensio-active agent 1 ~ 15%, pH value regulator 1 ~ 5%.
Description
(1) technical field
The present invention relates to a kind of glass-fiber reinforced thermo-setting resin technology, particularly the treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre.
(2) background technology
In mid-term the 1950's, Filament-wound Machine epoxy FRP pipes starts some field use in the U.S., in succession for line of pipes, oil pipe and sleeve pipe.Its High And Medium Pressure Frp Pipes is wound on core by the high strength glass fiber of the Low viscosity resin matrix that impregnated of high viscosifying power on Wiring apparatus by the angle set and laying, obtains through solidification, the demoulding, processing.Due to features such as its excellent corrosion resistance nature, high-durability, high-strength light and installation and maintenance convenience, solve the significant corrosion problems that steel oilfield tubulars exists, and contrast with other anticorrosive measure, comprehensive cost is low, and technical economic benefit is good.
The initial stage eighties, American Petroleum Institute (API) has successively formulated the corresponding API specification such as high-pressure glass steel wire pipe, oil pipe, sleeve pipe, from then on high-pressure glass fibre reinforced plastic pipe starts in field large-scale application such as the oil field of developed country, petrochemical industry, wherein the U.S. is in oilfield accumulative application fiber reinforced plastic pipe more than 100 ten thousand kilometers, and with annual 5% ~ 10% speed increase.It is anticorrosion that high-pressure glass fibre reinforced plastic pipe is applied to oil field, has been the mature technology that application is extremely successful in developed country.Concerning China oil field, it is also very promising technical products (according to China and U.S.'s glass reinforced plastic development contrast prediction: China should be use peak at 2010-2020, is rapid growth period at present).Water flood recovery and tertiary oil recovery technique are all promote the important factor of high-pressure glass fibre reinforced plastic pipe in field use.
As the major matrix material of epoxy pressure piping, the proportion of glass fibre in glass fiber reinforced plastics product, even up to 80%, therefore, can say that the performance of glass fibre decides the performance of final glass fiber reinforced plastics product.For epoxy pressure piping, first requiring that glass fiber yarn possesses excellent use smoothness, as requirements such as low filoplumes in winding process, is secondly good with epoxy resin compatibility, soak into fast and completely, the most important thing is that final fiberglass products possesses excellent mechanical property.General property requires following (content of glass fiber is 75%, for 2400tex):
● tensile property (according to ASTMD2343 testing method):
| Resin system | Epoxy resin |
| Tensile strength | ≥2400MPa |
| Tensile modulus | ≥78GPa |
● cutting performance (according to ASTMD2344 testing method):
| Resin system | Epoxy resin |
| Shearing resistance | ≥65MPa |
Need by developing a kind of novel treating compound: energy and target resin to possess excellent consistency, improve the effect of interface cohesion, to meet the index request of mechanical property for this reason.
(3) summary of the invention
Technical problem to be solved by this invention is to provide the treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre, adopt the direct yarn that this treating compound is produced, not only, good penetrability good with target resin compatible, and the mechanical property of goods can be made high, meet the requirement of standard.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
The invention discloses the treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre, described treating compound comprises coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and water, the solid masses of described treating compound accounts for 4 ~ 12% for the treatment of compound total mass, and surplus is water (water comprising raw material its own band adds the deionized water that preparation treating compound adds); Described coupling agent adopts silane coupling agent; Described lubricant adopts water miscible PEG series lubricant agent; Described membrane-forming agent is the blend of epoxy emulsion, organic siloxane modified epoxy emulsion and polyaminoester emulsion; Described tensio-active agent is the blend of nonionogenic tenside and cats product; Described pH value regulator is acid; The percentage that in described treating compound, following ingredients content accounts for treating compound solid masses with its quality is expressed as follows:
In the present invention, if component emulsion or solution form, its content is that the percentage that the quality of namely drying rear remainder with its solid masses accounts for treating compound solid masses represents.
Further, the preferred described treating compound of the present invention is made up of coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and water.
Further, in the preferred described treating compound of the present invention, each component concentration is as follows:
Further, in the preferred described treating compound of the present invention, each component concentration is as follows:
Again further, in the preferred described treating compound of the present invention, each component concentration is as follows:
The pH value for the treatment of compound of the present invention is 2 ~ 10, and preferable ph is 3 ~ 7.
Coupling agent of the present invention generally adopts the silane based coupling agents of band epoxy group(ing), vinyl or amino, and the available product grade of the silane coupling agent that the present invention is suitable for has A-172, A-174, A-1100, A-187 etc.The use of coupling agent; impaired in drawing process of fiber can be protected; and " bridge joint " effect played between glass fiber and matrix resin; therefore be the key affecting glass fiber strength and glass fiber reinforced plastics product intensity; suitable coupling agent is selected, and the epoxy pressure piping alkali free glass fibre direct yarn product produced can be made to have better mechanical property.The content 5 ~ 15% of silane coupling agent in the present invention, preferably 6 ~ 13%, more preferably 7 ~ 11%, further preferably 8 ~ 10%.
The lubricant that the present invention uses can adopt water miscible organic compound, and particularly PEG series lubricant agent, as PEG400, PEG600, PEG1000, PEG3000 etc.The use of lubricant is mainly and meets the lubricant effect of glass fibre in wire drawing, aftertreatment, use procedure, but too much lubricant can affect the convergency of glass fiber yarn, and the mechanical property of final glass fiber reinforced plastics product can be affected, therefore the content of lubricant described in the present invention is 5 ~ 20%, preferably 5 ~ 15%, more preferably 8 ~ 13%, further preferably 9 ~ 11%.
The blend that the tensio-active agent that the present invention uses is nonionogenic tenside and cats product.Wherein nonionogenic tenside adopts the one in polyethenoxy ether class, Microcrystalline Wax emulsion, chemical modification mineral oil emulsion; Cats product adopts the one in Fixanol, quaternary ammonium salt, amine salt.The content of preferred nonionic surfactants of the present invention is 1 ~ 11%, and the content of cation surface activating is 0.1 ~ 4.0%.Further, preferred surfactant of the present invention is the mixture of polyethenoxy ether class nonionogenic tenside and quaternary ammonium salt surface active agent.Further, the content of polyethenoxy ether class nonionogenic tenside is 5 ~ 7%, and the content of quaternary ammonium salt surface active agent is 1 ~ 3%.
Membrane-forming agent plays as the main component for the treatment of compound the effect protecting fiber, and plays conclusive impact to the physical strength of glass fibre end article, and therefore, the selection of membrane-forming agent is emphasis of the present invention.The membrane-forming agent that the present invention uses is epoxy emulsion, the combination of organic siloxane modified epoxy emulsion and polyaminoester emulsion.The present invention adopts the collocation of dissimilar emulsion to use, and except taking into account the convergency of glass fiber yarn, yarn matter, mainly considers the consistency with epoxy resin, thus improves the physical strength of glass fiber reinforced plastics product.The content summation of membrane-forming agent of the present invention is 65 ~ 80%, preferably 65 ~ 75%, and be more preferably 67 ~ 73.5%, be further preferably 69 ~ 72%.
The epoxy emulsion that the present invention uses is water-soluble epoxy resin emulsion or bisphenol A type epoxy resin emulsion, and molecular weight is 200 ~ 1200, is preferably the scope of 300 ~ 800, particle diameter of dispersing phase 0.2 ~ 2.0 μm.In the present invention, epoxy emulsion can be prepared voluntarily according to existing document or use commercial goods.The content of described epoxy emulsion is 10 ~ 45%, preferably 15 ~ 45%, more preferably 20 ~ 39%, further preferably 30 ~ 37%
The present invention use organic siloxane modified epoxy emulsion be by organo-siloxane monomer modified can be water-soluble modified epoxy resin emulsion, molecular resin amount is 800 ~ 2500, be preferably 1200 ~ 2000 scope, particle diameter of dispersing phase 0.2 ~ 2.0 μm.The present invention particularly preferably adopts the dual modified aqueous epoxy emulsion of KH570 and KH550, its preparation method can reference [Guo Wenlu, Lu's sweat is clear, Zhou Hongchun. the research (J) of the dual modified aqueous epoxy emulsion of organo-siloxane. and coatings industry, 09 phase in 2011].The content of described organic siloxane modified epoxy emulsion is 10 ~ 50%, preferably 12 ~ 49%, more preferably 15 ~ 45%, further preferably 20 ~ 30%.
The polyaminoester emulsion that the present invention uses is by the obtained polyester type of outer emulsification or internal emulsification method or polyether(poly)urethane resin emulsion, its relative molecular mass is 20000 ~ 40000, be preferably the scope of 25000 ~ 35000, particle diameter of dispersing phase 0.2 ~ 2.0 μm.Described polyaminoester emulsion can be prepared voluntarily according to literature method or use commercial goods.The content of described polyaminoester emulsion is 5 ~ 20%, preferably 8 ~ 16%, more preferably 9 ~ 13%, further preferably 11 ~ 12.5%.
PH value regulator of the present invention adopts acid, and organic acid or mineral acid, as used citric acid, acetic acid, formic acid, acetic acid etc.The effect of pH value regulator is mainly used for ancillary coupling agent dispersion and regulate the pH value of the treating compound prepared, and the pH value for the treatment of compound of the present invention is 2 ~ 10, and preferable ph is 3 ~ 7.
The compound method of the treating compound of the direct yarn of a kind of epoxy of the present invention pressure piping alkali free glass fibre comprises the following steps: the deionized water adding 40% ~ 50% of total amount in a clean container, and then the pH value regulator added in treating compound composition, abundant stirring is after 3 ~ 5 minutes, slowly add the silane coupling agent in treating compound composition again, Keep agitation 40 ~ 50 minutes; Lubricant in treating compound composition, tensio-active agent add container after abundant agitation and dilution at 5 times in the warm deionized water (40 ~ 50 DEG C) of its amount; In treating compound composition, membrane-forming agent adds container after adopting the water of 2 times of film forming dosage to dilute, if treating compound pH value can not reach optimum range, adds appropriate pH adjusting agent and carries out adjusting and stirring, until pH value reaches optimum range.
Combustible content (namely the coated amount on the glass fibers for the treatment of compound accounts for the ratio of the glass fiber quality) general control of glass fibre of the present invention is 0.3 ~ 1.0%, concrete value needs the performance according to raw material itself, the performance index reached from product needed and experimental results, the product that combustible content is produced 0.5 ~ 0.9%, physical strength can meet the demands.
Compared with prior art, treating compound of the present invention can, good penetrability good with resin compatible, and the mechanical property of goods can be made high, thus meets market and application demand.
(4) embodiment
By the following examples the present invention is specifically described, but content of the present invention is not by any restriction of following examples.
The each component for the treatment of compound that the embodiment of the present invention uses is as follows:
Described coupling agent uses epoxy silane coupling, and product grade is A-187;
Described lubricant uses PEG600;
Described membrane-forming agent epoxy resin latex, product grade is DSMJS129(manufacturer: Dutch DSM N. V.);
Described membrane-forming agent modified epoxy resin emulsion, adopts organo-siloxane KH570 and KH550(KH570 and KH550 content to account for the massfraction of epoxy resin than being 5:1) (the self-control of dual modified aqueous epoxy emulsion.Reference: Guo Wenlu, Lu Hanqing, Zhou Hongchun. the research (J) of the dual modified aqueous epoxy emulsion of organo-siloxane. coatings industry, 09 phase in 2011);
Described membrane-forming agent polyaminoester emulsion, product grade is PU400S(manufacturer: Bayer Material Science company limited);
Described nonionogenic tenside adopts alkylphenol polyoxyethylene OP;
Described cats product adopts organic quaternary ammonium salt 1831;
Described pH value regulator adopts acetic acid.
The quality proportioning of described nonionogenic tenside and cats product is 3:1.
Following table is concrete formulation examples and the concrete test result of the direct yarn of 2400Tex produced according to certain glass fibre production technique.In the embodiment of the present invention, the content of water accounts for 92% for the treatment of compound total mass, and numerical value is wherein each component accounts for treating compound solid masses per-cent in its solid content.
From above formula test case, we can therefrom find out, by the design to component and component concentration, we can obtain the treating compound meeted the requirements, wherein especially better with example 3,4 effect.Below be only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
The embodiment of the present invention is according to the technical characterstic of the direct yarn of epoxy pressure piping alkali free glass fibre, by the selection for the treatment of compound raw material, the optimization of formula, adopts suitable glass fibre production technique, produces the direct yarn product of the alkali free glass fibre meeting this domain requirement.
Claims (10)
1. the treating compound of the direct yarn of epoxy pressure piping alkali free glass fibre, described treating compound comprises coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and water, the solid masses of described treating compound accounts for 4 ~ 12% for the treatment of compound total mass, and surplus is water; Described coupling agent adopts silane coupling agent; Described lubricant adopts water miscible PEG series lubricant agent; Described membrane-forming agent is the blend of epoxy emulsion, organic siloxane modified epoxy emulsion and polyaminoester emulsion; Described tensio-active agent is the blend of nonionogenic tenside and cats product; Described pH value regulator is acid; The percentage that in described treating compound, following ingredients content accounts for treating compound solid masses with its quality is expressed as follows:
2. treating compound as claimed in claim 1, is characterized in that in described treating compound, following ingredients content is as follows:
3. treating compound as claimed in claim 1, is characterized in that in described treating compound, following ingredients content is as follows:
4. treating compound as claimed in claim 1, is characterized in that in described treating compound, following ingredients content is as follows:
5. the treating compound as described in one of Claims 1 to 4, is characterized in that: described treating compound is made up of coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value regulator and water.
6. the treating compound as described in one of Claims 1 to 4, is characterized in that: described silane coupling agent is the silane coupling agent of band epoxy group(ing), vinyl or amino.
7. the treating compound as described in one of Claims 1 to 4, is characterized in that: described organic siloxane modified epoxy emulsion is the dual modified aqueous epoxy emulsion of KH570 and KH550.
8. the treating compound as described in one of Claims 1 to 4, is characterized in that: described nonionogenic tenside adopts the one in polyethenoxy ether class, Microcrystalline Wax emulsion, chemical modification mineral oil emulsion; Described cats product adopts the one in Fixanol, quaternary ammonium salt, amine salt; The content of nonionogenic tenside is 1 ~ 11% for the treatment of compound solid masses, and the content of cats product is 0.1 ~ 4.0% for the treatment of compound solid masses.
9. treating compound as claimed in claim 8, is characterized in that: described tensio-active agent is the mixture of polyethenoxy ether class nonionogenic tenside and quaternary surfactant.
10. treating compound as claimed in claim 5, is characterized in that: described silane coupling agent is the silane coupling agent of band epoxy group(ing), vinyl or amino; Described organic siloxane modified epoxy emulsion is the dual modified aqueous epoxy emulsion of KH570 and KH550; Described tensio-active agent is the mixture of polyethenoxy ether class nonionogenic tenside and quaternary ammonium salt surface active agent, wherein the content of polyethenoxy ether class nonionogenic tenside is 1 ~ 11% for the treatment of compound solid masses, and the content of quaternary ammonium salt surface active agent is 0.1 ~ 4.0% for the treatment of compound solid masses.
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| CN201410013132.8A CN103771732B (en) | 2014-01-10 | 2014-01-10 | The treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre |
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| CN105152550B (en) * | 2015-08-10 | 2018-11-30 | 巨石集团有限公司 | A kind of size of the direct yarn of highly versatile alkali-free glass fibre |
| CN105551907A (en) * | 2015-12-15 | 2016-05-04 | 常熟市强盛冲压件有限公司 | High-voltage drop-out fuse tube |
| CN106242317B (en) * | 2016-07-15 | 2019-04-19 | 巨石集团有限公司 | Enhance the size of the direct yarn of polyurethane pultrusion alkali-free glass fibre |
| CN106277845B (en) * | 2016-07-15 | 2019-04-19 | 巨石集团有限公司 | Reinforced epoxy prepreg moves back treating compound for twistless roving with directly outer |
| CN106186730B (en) * | 2016-07-15 | 2019-04-19 | 巨石集团有限公司 | The size of FFU synthesis wooden sleeper alkali-free glass fibre yarn |
| CN106242318B (en) * | 2016-07-26 | 2019-04-19 | 巨石集团有限公司 | A kind of size and its preparation method and application |
| CN110066121B (en) * | 2019-06-11 | 2022-02-01 | 巨石集团有限公司 | Impregnating compound and preparation method and application thereof |
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| JPS5782148A (en) * | 1980-11-11 | 1982-05-22 | Fuji Fiber Glass Kk | Sizing agent for glass fiber |
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| CN101070426A (en) * | 2007-06-12 | 2007-11-14 | 巨石集团有限公司 | Glass-fiber reinforced fire-retardant polyamide resin composition |
| CN101100356A (en) * | 2007-06-12 | 2008-01-09 | 巨石集团有限公司 | Direct untwisted roving soaking agent |
| CN102241484A (en) * | 2011-04-12 | 2011-11-16 | 重庆国际复合材料有限公司 | Glass fiber sizing agent for roving cloth and preparation method thereof |
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