CN103880300A - Impregnating compound for alkali-free glass fiber direct roving for thermoplastic glass fiber reinforced pipeline - Google Patents
Impregnating compound for alkali-free glass fiber direct roving for thermoplastic glass fiber reinforced pipeline Download PDFInfo
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- CN103880300A CN103880300A CN201410043648.7A CN201410043648A CN103880300A CN 103880300 A CN103880300 A CN 103880300A CN 201410043648 A CN201410043648 A CN 201410043648A CN 103880300 A CN103880300 A CN 103880300A
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Abstract
The invention relates to an impregnating compound for alkali-free glass fiber direct roving for a thermoplastic glass fiber reinforced pipeline. The impregnating compound comprises a silane coupling agent, a PEG (polyethylene glycol) lubricant, a film forming agent, a cationic surface active agent, a pH value regulator and water, the solid content of the impregnating agent is 6-14%; the film forming agent is a blend of epoxy emulsion, polyurethane emulsion and epoxy-modified acrylate emulsion; the pH value regulator is an acid; according to mass percentage of the impregnating compound, the impregnating compound comprises the following components in percentage by weight of the solid impregnating compound: 6-20% of coupling agent, 5-20% of lubricant, 20-40% of epoxy emulsion, 10-30% of polyurethane emulsion, 15-25% of epoxy-modified acrylate emulsion, 65-75% of film forming agent, 0.5-8% of surface active agent and 2-7% of pH value regulator. The direct twistless roving produced by adopting the impregnating compound not only has ultrahigh breakage strength, but also is good in wear resistance and generates less feathers, thus meeting the design indexes of the thermoplastic glass fiber reinforced pipeline.
Description
(1) technical field
The present invention relates to the treating compound of the direct yarn of a kind of fiber glass reinforced thermoplastics's pipeline alkali free glass fibre.
(2) background technology
Fiber glass reinforced thermoplastics's pipeline is by after thermoplastics heating and melting, compound with n layer glass fibre, and pressurization is wound into pipeline goods, belongs to glass filament reinforced plastics technical field.Compared with metallic conduit, fiber glass reinforced thermoplastics's pipeline has that lightweight, high-strength, inner wall smooth, frictional coefficient are little, antiseepage, corrosion-resistant, heat insulation, insulation, can heat the advantages such as shaping welding, is widely used in the every field of the national economy such as oil, chemical industry, electric power, transportation, water supply and drainage.In the time that working temperature is-60 ℃ to+100 ℃, can be for storing and carry various organic and inorganic mediums.
Different from thermoset frp pipeline, fiber glass reinforced thermoplastics's pipeline does not need glass fibre and resin compatible, and its ducted glass fibre is to wrap by thermoplastic resin the enhancement reaching.Therefore,, in fiber glass reinforced thermoplastics's piping design, glass fibre must possess dry yarn breaking tenacity and the low filoplume performance of superelevation.General property requires following (take 600tex as example):
● breaking tenacity
| Project | Testing standard | Unit | Indication range |
| Breaking tenacity | ISO3341 | N/tex | ≥0.6 |
Need by developing a kind of novel treating compound: make glass fibre possess breaking tenacity and the low filoplume performance of superelevation, to meet the design objective of fiber glass reinforced thermoplastics's pipeline 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 fiber glass reinforced thermoplastics's pipeline alkali free glass fibre, the direct roving that adopts this treating compound to produce, not only possesses the breaking tenacity of superelevation, and wear resistance is good, filoplume is few, thereby meets the design objective of fiber glass reinforced thermoplastics's pipeline.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
The invention provides the treating compound of the direct yarn of a kind of fiber glass reinforced thermoplastics's pipeline alkali free glass fibre, described treating compound comprises coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value conditioning agent and water, and the solid content of described treating compound is 6～14%; Described coupling agent adopts silane coupling agent; Described lubricant adopts PEG series lubricant agent; Described membrane-forming agent is the blend of epoxy emulsion, polyaminoester emulsion and epoxide modified acrylic ester emulsion; Described tensio-active agent is cats product; Described pH value conditioning agent is acid; The percentage that in described treating compound, the content of following each component accounts for treating compound solid masses with its quality is expressed as follows:
Further, the percentage that in the preferred described treating compound of the present invention, the content of following each component accounts for treating compound solid masses with its quality is expressed as follows:
Further, the percentage that in the preferred described treating compound of the present invention, the content of each component accounts for treating compound solid masses with its quality is expressed as follows:
The pH value for the treatment of compound of the present invention is controlled at 2～10, and preferably pH value is controlled at 3～7.
The preferred described treating compound of the present invention is made up of coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value conditioning agent and water.
In the present invention, if component emulsion or solution form, its content is that the percentage that the quality of drying rear remainder with its solid masses accounts for treating compound solid masses represents.
Coupling agent of the present invention is preferably with epoxy group(ing), vinyl or amino silane coupling agent, and the applicable available product grade of silane coupling agent of the present invention has A-151, A-172, A-174, A-1100, A-1126, A-187 etc.The use of coupling agent can reduce or prevent impaired in drawing process of fiber, participates in the film formation reaction between other organic compound in glass fibre and treating compound simultaneously.Therefore, suitable coupling agent is selected, and is one of key factor improving the direct yarn breaking tenacity of glass fibre.In the present invention, the content of silane coupling agent is 6～20%, preferably 8～16%, more preferably 9.5～12.5%.
The lubricant that the present invention uses can adopt water miscible organic compound, particularly PEG series lubricant agent, as PEG400, PEG600, PEG1000, PEG3000, PEGMO etc., the use of lubricant can effectively improve the hygrometric state lubricant effect in glass fibre moulding process, increases flexibility and the tapability of yarn bundle.In the present invention, described lubricant content is 5～20%, preferably 8～16%, more preferably 9.5～13.5%.
The tensio-active agent that the present invention uses is cats product, can adopt the one in Fixanol, quaternary ammonium salt, amine salt, such as described quaternary ammonium salt can be selected the commodity of the models such as 1631,1827,1831,1227.In the present invention, described surfactant content is 0.5～8%, preferably 1～6%, more preferably 2.5～4.5%.
Membrane-forming agent plays the effect of protection fiber as the main component for the treatment of compound, and the physical strength of glass fibre end article is played to conclusive impact, and therefore, the selection of membrane-forming agent is emphasis of the present invention.The membrane-forming agent that the present invention uses is the combination of epoxy emulsion, polyaminoester emulsion and epoxide modified acrylic ester emulsion, except taking into account the convergency, wear resistance of glass fiber yarn, be mainly the breaking tenacity of considering reinforcing glass silvalin, thereby meet the design objective of fiber glass reinforced thermoplastics's pipeline.
Epoxy emulsion of the present invention can be water-soluble epoxy resin, bisphenol A-type or bisphenol f type epoxy resin emulsion, and molecular weight is 360～2000, is preferably 600～1500 scope, particle diameter of dispersing phase 0.2～2.0 μ m.The present invention uses relative molecular mass compared with circlet oxygen emulsion, can make glass fiber yarn matter soft, but convergency is poorer.In the present invention, described epoxy emulsion content is 20～40%, preferably 25～35%, more preferably 28～32%.
Polyaminoester emulsion of the present invention is polyester type or the polyether(poly)urethane resin emulsion making by outer emulsification or internal emulsification method, its relative molecular mass is 50000～80000, be preferably 60000～70000 scope, particle diameter of dispersing phase 0.2～2.0 μ m.Because polyaminoester emulsion has the urethano group of high polarity and high chemical property, the large thermoplastic material of relative unreactiveness is had to very strong cohesive force and Interface adhesive strength.Facts have proved simultaneously, in treating compound formula, as long as add a small amount of polyaminoester emulsion, can effectively improve convergency and the wear resistance of glass fiber yarn, nor be The more the better, because too much polyaminoester emulsion can increase the stiffness of glass fibre, thereby bring the disadvantageous effects such as crinosity plumage.In the present invention, described polyaminoester emulsion content is 10～30%, preferably 15～25%, more preferably 17～22%.
Epoxide modified acrylic ester emulsion of the present invention is the epoxide modified acrylic ester emulsion by adopting epoxy resin modification acrylate method to make, its relative molecular mass is 4000～20000, be preferably 6000～15000 scope, particle diameter of dispersing phase 0.2～2.0 μ m.Described epoxide modified acrylic ester emulsion can reference literature method be prepared voluntarily, for example document [Yang Qin, Yan Wei. the synthesising process research (J) of epoxy modification acrylate emulsion. Chinese tackiness agent, 05 phase in 2003] record method.Relative molecular weight is large, cohesive force is strong owing to having for epoxide modified acrylic ester emulsion, gives the intensity of the better convergency of glass fiber yarn and Geng Gao.In the present invention, described epoxide modified acrylic ester emulsion content is 15～25%, preferably 16～22%, more preferably 18.5～21%.
In the present invention, the total content of described membrane-forming agent is 65～75%, preferably 67～72%, more preferably 69～70%.
PH adjusting agent of the present invention adopts acid, organic acid or mineral acid all can, as used citric acid, acetic acid, formic acid, acetic acid etc.The effect of pH adjusting agent is mainly the pH value of disperseing and regulate the treating compound preparing for auxiliary coupling agent, and the pH value for the treatment of compound of the present invention is 2～10, and preferably pH value is 3～7.
The present invention also provides the compound method of described treating compound, comprise the following steps: in a clean container, add 40%～50% deionized water of total amount, and then add pH value conditioning agent, fully stir after 3～5 minutes, slowly add again silane coupling agent, continue to stir 40～50 minutes; Lubricant, tensio-active agent fully add container after agitation and dilution in 5 times of warm deionized waters to its amount (40～50 ℃); Membrane-forming agent adds container after adopting 2 times of water of film forming dosage to dilute; If treating compound pH value can not reach optimum range, then add appropriate acid adjust and stir, until pH value reaches optimum range.
The combustible content of glass fibre of the present invention (being the ratio that treating compound is coated on amount on glass fibre and accounts for glass fibre quality) general control is 0.45～1.2%, concrete value need to be according to the performance of raw material itself, the performance index that reach from product needed and experimental results, combustible content is at 0.7～1.0% product of producing, and breaking tenacity can meet the demands.
Compared with prior art, the glass fibre breaking tenacity that treating compound of the present invention is produced is high, and in use procedure, filoplume is few, thereby 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 subject to any restriction of following examples.
The each component for the treatment of compound that the embodiment of the present invention is used is as follows:
Described coupling agent uses methyl-propyl acyloxy silane coupling agent, and product grade is A-174;
Described lubricant uses PEGMO, product grade Emerest2646(manufacturer: COSNIS);
Described membrane-forming agent epoxy resin latex, product grade is DSM JS129(manufacturer: Dutch DSM N. V.);
Described membrane-forming agent polyaminoester emulsion, product grade is PU400S(manufacturer: Bayer Material Science company);
The epoxide modified acrylic ester emulsion of described membrane-forming agent is self-control, preparation method referring to [Yang Qin, Yan Wei. the synthesising process research (J) of epoxy modification acrylate emulsion. Chinese tackiness agent, 2003 years 05 phases].Concrete preparation method is: select the mix monomer of the butyl acrylate (Tg is-55 ℃) of mass ratio 80% and the methyl methacrylate (Tg is 105 ℃) of mass ratio 20%, and adopt 2% N mono-n-methylolacrylamide of monomer total amount as cross-linking monomer; Epoxy resin adopts E-44, accounts for 8.5% of monomer total amount; Emulsifying agent adopts the OP-10 of non-ionic type and the Sodium dodecylbenzene sulfonate compound emulsifying agent of anionic, accounts for 9% of monomer total amount, wherein negatively charged ion: nonionic=1.44:1; Initiator is ammonium persulphate, and consumption is monomer mass 0.66%, adopt with monomer mixing and emulsifying after mode add.The acrylic ester emulsion relative molecular mass 6000～15000 that described self-control is epoxide modified, particle diameter of dispersing phase 0.2～2.0 μ m.
Described cats product adopts organic quaternary ammonium salt 1631;
Described pH value conditioning agent adopts acetic acid.
The concrete test result of the direct yarn of 600tex that following table is produced for concrete formulation examples with according to certain glass fibre production technique.In the embodiment of the present invention, the content of water accounts for 90% for the treatment of compound total mass, numerical value is wherein each component concentration, and the percentages that component concentration accounts for treating compound solid masses with its quality (or solid masses) represents, wherein the quality of emulsion or solution is in its solid masses.
| Component | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Coupling agent | 8 | 9 | 10.5 | 12 | 13 | 14 |
| Lubricant | 16 | 14 | 12 | 10 | 9 | 8 |
| Epoxy emulsion | 26 | 27 | 29 | 31 | 32.5 | 34 |
| Polyaminoester emulsion | 25 | 23.5 | 21 | 18 | 16.5 | 15 |
| Epoxide modified acrylic ester emulsion | 16.5 | 18.3 | 19 | 20.8 | 21.2 | 22 |
| Tensio-active agent | 6 | 5 | 4 | 3 | 2 | 1 |
| PH adjusting agent | 2.5 | 3.2 | 4.5 | 5.2 | 5.8 | 6 |
| Formula solids content ratio adds up to | 100 | 100 | 100 | 100 | 100 | 100 |
| The combustible content of product | 0.69 | 0.76 | 0.81 | 0.85 | 0.92 | 0.93 |
| The linear density (tex) of product | 602 | 598 | 599 | 604 | 601 | 601 |
| Precursor boundling state | Good | Good | Good | Good | Good | Poor |
| Yarn matter | Firmly | Slightly hard | Moderate | Moderate | Moderate | Softer |
| Breaking tenacity (N/tex) | 0.54 | 0.58 | 0.65 | 0.66 | 0.58 | 0.56 |
| Filoplume (mg/kg) | 65 | 25 | 10 | 12 | 10 | 36 |
From above formula test case, we can therefrom find out, by the design to component concentration, and the treating compound that we can obtain meeting the requirements, wherein especially better with example 3,4 effects.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.
Claims (9)
1. a treating compound for the direct yarn of alkali free glass fibre for fiber glass reinforced thermoplastics's pipeline, described treating compound comprises coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value conditioning agent and water, the solid content of described treating compound is 6～14%; Described coupling agent adopts silane coupling agent; Described lubricant adopts PEG series lubricant agent; Described membrane-forming agent is the blend of epoxy emulsion, polyaminoester emulsion and epoxide modified acrylic ester emulsion; Described tensio-active agent is cats product; Described pH value conditioning agent is acid; The percentage that in described treating compound, the content of following each component 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: the percentage that in described treating compound, the content of following each component accounts for treating compound solid masses with its quality is expressed as follows:
3. treating compound as claimed in claim 1, is characterized in that: the percentage that in described treating compound, the content of following each component accounts for treating compound solid masses with its quality is expressed as follows:
4. the treating compound as described in one of claim 1～3, is characterized in that: described coupling agent is with epoxy group(ing), vinyl or amino silylation coupling agent.
5. the treating compound as described in one of claim 1～3, is characterized in that: described epoxy emulsion is water-soluble, bisphenol A-type or bisphenol f type epoxy resin emulsion, and the molecular weight of epoxy resin is 360～2000, particle diameter of dispersing phase 0.2～2.0 μ m; Described polyaminoester emulsion is polyester type or the polyether(poly)urethane resin emulsion making by outer emulsification or internal emulsification method, and the relative molecular mass of urethane resin is 50000～80000, particle diameter of dispersing phase 0.2～2.0 μ m; In described epoxide modified acrylic ester emulsion, the relative molecular mass of epoxide modified acrylate resin is 4000～20000, particle diameter of dispersing phase 0.2～2.0 μ m.
6. the treating compound as described in one of claim 1～3, is characterized in that: described cats product adopts the one in Fixanol, quaternary ammonium salt, amine salt.
7. the treating compound as described in one of claim 1～3, is characterized in that: described pH adjusting agent adopts acid, and the pH value of described treating compound is controlled at 2～10.
8. the treating compound as described in one of claim 1～3, is characterized in that:
Described coupling agent is with epoxy group(ing), vinyl or amino silylation coupling agent;
Described epoxy emulsion is water-soluble, bisphenol A-type or bisphenol f type epoxy resin emulsion, and the molecular weight of epoxy resin is 360～2000, particle diameter of dispersing phase 0.2～2.0 μ m; Described polyaminoester emulsion is polyester type or the polyether(poly)urethane resin emulsion making by outer emulsification or internal emulsification method, and the relative molecular mass of urethane resin is 50000～80000, particle diameter of dispersing phase 0.2～2.0 μ m; In described epoxide modified acrylic ester emulsion, the relative molecular mass of epoxide modified acrylate resin is 4000～20000, particle diameter of dispersing phase 0.2～2.0 μ m.
Described cats product adopts the one in Fixanol, quaternary ammonium salt, amine salt.
Described pH adjusting agent adopts acid, and the pH value of described treating compound is controlled at 2～10.
9. treating compound as claimed in claim 8, is characterized in that: described treating compound is made up of coupling agent, lubricant, membrane-forming agent, tensio-active agent, pH value conditioning agent and water.
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| CN107365091A (en) * | 2017-08-02 | 2017-11-21 | 山东玻纤集团股份有限公司 | One kind enhancing thermoplasticity short glass fiber size |
| CN115404584A (en) * | 2021-05-27 | 2022-11-29 | 旭化成株式会社 | Glass yarn, method for producing glass cloth, and glass cloth |
| CN114735947A (en) * | 2022-02-25 | 2022-07-12 | 陕西汇友友基新材料有限公司 | Preparation method of alkali-resistant glass fiber impregnating compound for replacing steel fiber |
| CN114735950A (en) * | 2022-02-25 | 2022-07-12 | 陕西汇友友基新材料有限公司 | Glass fiber impregnating compound special for mica cloth |
| CN114735947B (en) * | 2022-02-25 | 2024-02-20 | 陕西汇友友基新材料有限公司 | Preparation method of alkali-resistant glass fiber impregnating compound for replacing steel fibers |
| CN114735950B (en) * | 2022-02-25 | 2024-05-28 | 陕西汇友友基新材料有限公司 | Glass fiber impregnating compound special for mica cloth |
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