CN115215561A - Glass fiber impregnating compound and preparation method and application thereof - Google Patents
Glass fiber impregnating compound and preparation method and application thereof Download PDFInfo
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- CN115215561A CN115215561A CN202210661962.6A CN202210661962A CN115215561A CN 115215561 A CN115215561 A CN 115215561A CN 202210661962 A CN202210661962 A CN 202210661962A CN 115215561 A CN115215561 A CN 115215561A
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- glass fiber
- lubricant
- coupling agent
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- impregnating compound
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 239000004952 Polyamide Substances 0.000 claims abstract description 20
- 229920002647 polyamide Polymers 0.000 claims abstract description 20
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 16
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 16
- 239000000314 lubricant Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000007822 coupling agent Substances 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 28
- 238000004513 sizing Methods 0.000 claims description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Chemical group 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical group 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 238000012545 processing Methods 0.000 abstract description 12
- 239000004677 Nylon Substances 0.000 abstract description 6
- 229920001778 nylon Polymers 0.000 abstract description 6
- 239000000805 composite resin Substances 0.000 abstract description 5
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
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- 238000012360 testing method Methods 0.000 description 9
- 206010020112 Hirsutism Diseases 0.000 description 7
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- 238000005452 bending Methods 0.000 description 5
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- 238000001746 injection moulding Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000007865 diluting Methods 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
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- 238000005299 abrasion Methods 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 239000011208 reinforced composite material Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
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Images
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
- C03C25/465—Coatings containing composite materials
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The invention belongs to the technical field of glass fiber surface treatment, and particularly relates to a glass fiber impregnating compound and a preparation method and application thereof. According to the glass fiber impregnating compound provided by the invention, through the matching of the components and the adjustment of the using amount, especially the matching use of different types of film forming agents and the selection of waterborne polyurethane with different molecular weights as a main film forming agent and the selection of polyamide emulsion as an auxiliary film forming agent, the high temperature resistance of the impregnating compound is improved, so that the high temperature resistance of the impregnating compound can meet the processing temperature requirement of a high temperature resistant thermoplastic nylon resin composite material, and the compatibility and the bonding capability between glass fibers and base material resin are obviously improved.
Description
Technical Field
The invention belongs to the technical field of glass fiber surface treatment, and particularly relates to a glass fiber impregnating compound and a preparation method and application thereof.
Background
The high-performance glass fiber has higher mechanical property, stronger corrosion resistance, higher heat resistance, excellent dielectric and electrical insulation performance and the like compared with the common glass fiber, is used as a reinforced base material of a high-performance composite material, and is mainly used in the national defense fields of aviation, aerospace, weaponry, nuclear industry and the like.
The glass fiber is an inorganic substance with strong polarity, and the main component of the glass fiber is SiO 2 The resin is a high molecular polymer, the two materials are completely incompatible, and when the glass fiber is used as a reinforcing material of the resin, the interface bonding performance with the resin is poor, so that one of the key technologies of the high-performance glass fiber reinforced composite material is a sizing agent technology for determining the properties such as a material processing technology and a composite material interface.
The sizing agent is a glass fiber surface treatment agent, and the glass fiber is treated by a water-based sizing agent after flowing out of a bushing, so that the glass fiber has good textile processing performance and excellent mechanical properties of a composite material. Different impregnating compounds endow the glass fibers with different properties, and various twistless rovings for spinning and weaving have good spinning use performance and good compatibility with base resin so as to meet different product requirements. Therefore, the development of the sizing agent suitable for the high-performance glass fiber and the composite material thereof is very important.
The processing method of the high-temperature-resistant thermoplastic nylon resin composite material is generally that injection molding is carried out after double-screw extrusion granulation, taking the most typical PA6T as an example, the melting point of industrial PA6T is as high as 310-320 ℃, and the heat resistance of a conventional film forming agent cannot reach the standard, meanwhile, because the color of the PA6T is white, most composite material products also have requirements on the color, if a large number of components with poor temperature resistance exist in the glass fiber impregnating compound, the high-temperature-resistant thermoplastic nylon resin composite material cannot play a role in promoting and protecting the combination of base material resin and fibers, but can influence the combination performance and appearance performance of the resin and the glass fibers due to the generation of carbon residue. In addition, when the properties of the glass fiber and the matrix resin reach the optimal state, the interfacial bonding capability of the composite material determines whether the stress transmission between the glass fiber and the matrix resin is good or not, and the difference has an important influence on the mechanical properties of the composite material.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the heat resistance of the glass fiber impregnating compound in the prior art cannot meet the temperature requirement for processing high-temperature-resistant thermoplastic nylon resin composite materials, the interface bonding capacity of glass fibers and base resin needs to be further improved and the like, and provides the glass fiber impregnating compound, and a preparation method and application thereof.
Therefore, the invention can provide the following technical scheme:
the invention provides a glass fiber impregnating compound which comprises the following components in percentage by mass in effective content:
3-8% of film forming agent, 0.5-1.5% of lubricant and 0.5-1.2% of coupling agent;
wherein the film-forming agent comprises 2-4% of low molecular weight aqueous polyurethane with the number average molecular weight of 400-1500 and 0.5-2% of high molecular weight aqueous polyurethane with the number average molecular weight of 2000-4000, based on the total mass of the glass fiber sizing agent; 0.5-2% of water-based polyamide emulsion;
the coupling agent is a mixture of a silane coupling agent containing a benzene ring and a silane coupling agent containing amino and/or epoxy functional groups.
Optionally, the aqueous polyamide emulsion is an aqueous emulsion prepared by taking polyamide resin as a raw material and emulsifying.
Optionally, the lubricant comprises 0.5-1.2% of non-ionic lubricant based on the total mass of the glass fiber impregnating compound; 0.1-0.3% of ionic lubricant.
Optionally, the non-ionic lubricant is at least one of a mineral oil lubricant, an ester lubricant, a long-chain flexible benzene ring-containing lubricant, a silicone lubricant or an amide lubricant;
and/or the ionic lubricant is at least one of lubricant 6760L and lubricant 8760.
Optionally, the coupling agent is a silane coupling agent with a thermal decomposition temperature of above 300 ℃;
optionally, the coupling agent comprises 0.4-0.8% of silane coupling agent containing benzene ring and 0.1-0.4% of silane coupling agent containing amino and/or epoxy functional group based on the total mass of the glass fiber sizing agent.
Optionally, the total solid content of the glass fiber impregnating compound is 5-6wt%;
and/or the pH value of the glass fiber impregnating compound is 5-7.
Optionally, adjusting the pH of the glass fiber impregnating compound by using a pH regulator;
optionally, the pH adjuster is an organic acid;
optionally, the organic acid is at least one of acetic acid, formic acid, succinic acid or citric acid.
Optionally, the glass fiber impregnating compound contains water in the balance.
The invention also provides a preparation method of the glass fiber impregnating compound, which comprises the following steps:
s1, dispersing a coupling agent into water, and adjusting the pH value to obtain a coupling agent solution;
s2, mixing a film forming agent and a lubricant, mixing with the coupling agent solution, and adjusting the pH value to obtain the glass fiber impregnating compound;
optionally, the amount of water used in the step S1 is 4-6 times of the mass of the coupling agent;
optionally, the pH is adjusted to 5-7 in both steps S1 and S2.
Typically, but not limitatively, the specific operation of the method for preparing the glass fiber sizing agent can be as follows:
(1) Adding water with the dosage 5 times of that of the coupling agent into the coupling agent, adding a pH regulator to adjust the pH to 5-7, and fully mixing until the coupling agent is uniformly dispersed to obtain a coupling agent solution;
(2) And fully dispersing the film forming agent and the lubricant into water, uniformly mixing the film forming agent and the lubricant with the coupling agent solution, and finally adjusting the pH of the mixed solution to 5-7 by using a pH regulator to obtain the glass fiber impregnating compound.
Further preferably, the preparation method of the glass fiber impregnating compound may be:
(1) Adding the coupling agent into a first mixing container, adding deionized water with the mass of 5 times that of the coupling agent, stirring, adding a pH regulator until the pH of the aqueous solution is 5-7, and continuously stirring until the liquid surface is clear to obtain a coupling agent solution;
(2) Adding low molecular weight waterborne polyurethane and high molecular weight waterborne polyurethane into a second mixing container, adding deionized water with the mass 5 times that of the total amount of polyurethane emulsion, and uniformly stirring;
(3) Fully diluting the water-based polyamide emulsion with deionized water 8 times of the mass of the water-based polyamide emulsion, adding the diluted water-based polyamide emulsion into a second mixing container, and uniformly stirring;
(4) Fully diluting the lubricant with deionized water 10 times of the weight of the lubricant, adding the diluted lubricant into a second mixing container, and uniformly stirring;
(5) And adding the silane coupling agent solution in the first mixing container into a second mixing container, uniformly stirring, adding the rest deionized water, and adjusting the pH value to 5-7 to obtain a finished impregnating compound.
The invention also provides an application of the glass fiber impregnating compound in preparation of a thermoplastic high-temperature-resistant composite material.
Optionally, the thermoplastic high-temperature resistant composite material is a composite material of glass fiber and base resin,
optionally, the base resin is PA6 resin;
optionally, the PA6 resin is PA6T resin.
The technical scheme of the invention has the following advantages:
the glass fiber impregnating compound provided by the invention has the advantages that through the matching among the components and the adjustment of the dosage, particularly the selection of different types of film forming agents and the matching use of specific coupling agents, the surface of the glass fiber is endowed with good compatibility with matrix resin, and the compatibility and the interface bonding capability between the glass fiber and the matrix resin are obviously improved. Specifically, the water-based polyurethane with different molecular weights is used as a main film forming agent, the water-based polyamide emulsion is used as an auxiliary film forming agent, the high-temperature resistance of the impregnating compound is improved, the temperature requirement for processing of a high-temperature-resistant thermoplastic nylon resin composite material can be met, the water-based polyurethane has good high-temperature resistance, and the matching performance of glass fibers and base resin can be improved while the film forming performance of the whole impregnating compound is improved by the water-based polyamide emulsion. The high molecular weight polyurethane can provide higher yarn coating rate, effectively improve the wear resistance of the glass fiber, and the low molecular weight polyurethane can improve the softness of the glass fiber and the elasticity of a glass fiber surface sizing agent film, play a part of roles in improving the lubricating performance and contribute to improving the fatigue resistance of the glass fiber; meanwhile, the polyurethane has more strong polar groups, the viscosity of the film is higher after the film is formed, a layer of compact protective film is easily formed on the surface of the glass fiber, the glass fiber is isolated from the outside, water is effectively prevented from entering microcracks of the glass fiber, and the processing performance of the glass fiber is further improved. The invention adopts different types of film forming agents to match and use, not only endows the glass fiber and the matrix resin with good compatibility and interface bonding performance, but also improves the fatigue resistance of the glass fiber yarn on the basis of ensuring the softness of the glass fiber yarn. Meanwhile, the water-based polyamide emulsion is added into the formula, and the polyamide emulsion has good film-forming property, excellent cohesiveness and abrasion resistance, and excellent temperature resistance, gives the glass fiber yarn certain rigidity, has good compatibility with nylon base material resin, and improves the combination degree of the glass fiber yarn and the base material resin. The silane coupling agent at least needs a high-temperature-resistant silane coupling agent containing a benzene ring, and also comprises a silane coupling agent containing amino or epoxy functional groups, and the silane coupling agent has a structure similar to that of a resin substrate due to the existence of the amino/epoxy functional groups and the benzene ring, so that the silane coupling agent is very suitable for being used as a bridge for combining resin and glass fiber, and meanwhile, the structure of the silane coupling agent is similar to that of an auxiliary film-forming agent polyamide emulsion, so that a net structure can be formed by better mutual combination, and the combination performance with the substrate resin is improved. In addition, the invention can enhance the adhesion of the film forming agent and the glass fiber by selecting the specific coupling agent, and can reduce the hairiness amount and broken ends of the glass fiber in the processing process. Compared with the prior art, the components of the formula of the impregnating compound are simpler, the preparation process is simplified, the formula endows the glass fiber with good processing performance, the compatibility with thermoplastic high-temperature-resistant base material resin is good, the mechanical property of the glass fiber composite material is improved, the color difference of the composite material is reduced, and the novel product, namely the glass fiber reinforced composite material, also has better strength and modulus.
The glass fiber impregnating compound provided by the invention has the effects of dry lubrication and wet lubrication by further limiting the lubricant, has the effects of lubricating the surface of the glass fiber and reducing abrasion in a wet state (in a wire drawing process) and a dry state (strand drawing and spinning processing), and simultaneously has a promoting effect on the combination of the glass fiber and the base resin, thereby overcoming the defect that the use of the conventional lubricant is not beneficial to the combination of the glass fiber and the base resin. The non-ionic lubricant can reduce the generation of broken filaments and improve the wear resistance of the fiber. The non-ionic lubricant is preferably mineral oil type, ester type, benzene ring type, organosilicon type or amide type lubricant, has a lubricating effect, can reduce a contact angle between a wetting system and the surface of the glass fiber, can play a wetting effect at the same time, has excellent high temperature resistance, and can still protect the glass fiber in the extrusion process of the composite material and prevent burrs from being generated when the non-ionic lubricant is mixed with the base resin at high temperature. Meanwhile, a small amount of high-efficiency ionic lubricant is added to be used as dry lubrication to reduce friction and static electricity generated during spinning of the fibers.
The glass fiber impregnating compound provided by the invention has the advantages that the acid dosage is determined according to the type and dosage of the coupling agent, the prepared impregnating compound is convenient to store and apply under a certain pH condition, and the acid environment with the pH value of 5-7 is better.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a photograph of a yarn in an experimental example of the present invention, from left to right, a non-thermoplastic yarn (made by itself), a thermoplastic yarn (available from Taber) suitable for a general thermoplastic resin, and a yarn prepared by using the treating compound of example 1.
As can be seen from the figure, the product provided by the embodiment 1 of the invention has small color change after high-temperature injection molding and good high-temperature resistance.
FIG. 2 is a drawing showing an apparatus used for measuring the amount of hairiness in the experimental example of the present invention.
Reference numerals:
(1) A creel; (2) yarn groups; (3) a motor; (4) a winding device; (5) yarns; and (6) rubbing points.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Examples and comparative examples
In the following examples and comparative examples, the sources of the respective raw materials are as follows: the low molecular weight water-based polyurethane emulsion adopts U-series water-based polyurethane of Mackemen company, the effective content is 30wt%, and the number average molecular weight is 400-1500; the high-molecular aqueous polyurethane emulsion is a self-made emulsion prepared by a medium material technology, the product type is 240-3, the effective content is 25wt%, and the number average molecular weight is 2000-4000; the water-based polyamide emulsion is supplied by Mackemen, is in a commercial model of pa845H, and has an effective content of 30wt%; the lubricant TR-2382 is a medium material produced by science and technology, and the effective content is 99wt%; the effective content of the ionic lubricant 6760L provided by Kekai is 99wt%; coupling agents Y-9669, A-1100, A-187 are all provided by Meiji, inc., with an effective content of 99% by weight.
In each of the examples and comparative examples, the chemical composition of the glass fiber sizing agent is shown in the following table in terms of effective content:
TABLE 1
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Low-molecular water-based polyurethane emulsion U5 | 2.5％ | 2％ | 3％ | 2.5％ | 2.5％ | 2.5％ |
| High molecular polyurethane emulsion 240-3 | 1.2％ | 2％ | 1.5％ | 1.2％ | 1.2％ | 1.2％ |
| Aqueous polyamide emulsion | 0.8％ | 0.8％ | 0.8％ | 0.8％ | 0.8％ | 0.8％ |
| Lubricant TR-2382 | 0.7％ | 0.7％ | 0.7％ | 0.5％ | 0.8％ | 0.7％ |
| Lubricant 6760L | 0.2％ | 0.2％ | 0.2％ | 0.1％ | 0.3％ | 0.2％ |
| Coupling agent Y-9669 | 0.6％ | 0.6％ | 0.6％ | 0.6％ | 0.6％ | 0.4％ |
| Coupling agent A-187 | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.1％ |
| pH | 6.3 | 6.3 | 6.3 | 6.3 | 6.3 | 6.3 |
| Components | Example 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Low-molecular water-based polyurethane emulsion | 2.5％ | 3.0％ | 3.7％ | / | 3.3％ | 2.5％ |
| High-molecular polyurethane emulsion | 1.2％ | 1.5％ | / | 3.7％ | / | 1.2％ |
| Aqueous polyamide emulsion | 0.8％ | / | 0.8％ | 0.8％ | 1.2％ | 0.8％ |
| Lubricant TR-2382 | 0.7％ | 0.8％ | 0.7％ | 0.7％ | 0.7％ | 0.7％ |
| Lubricant 6760L | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ |
| Coupling agent Y-9669 | 0.8％ | 0.6％ | 0.6％ | 0.6％ | 0.6％ | / |
| Coupling agent A-187 | 0.4％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.8 |
| pH | 6.3 | 6.3 | 6.3 | 6.3 | 6.3 | 6.3 |
The preparation methods of the glass fiber sizing agents provided in the above examples and comparative examples are as follows:
(1) Adding the coupling agent into a first mixing container, adding deionized water with the mass of 5 times that of the coupling agent, stirring, adding a pH regulator until the pH of the aqueous solution is 5-7, and continuously stirring until the liquid surface is clear to obtain a coupling agent solution;
(2) Adding the low molecular weight aqueous polyurethane emulsion and the high molecular weight aqueous polyurethane emulsion into a second mixing container, adding deionized water with the mass 5 times that of the polyurethane emulsion, and uniformly stirring;
(3) Fully diluting the water-based polyamide emulsion with deionized water 8 times the weight of the water-based polyamide emulsion, adding the diluted water-based polyamide emulsion into a second mixing container, and uniformly stirring;
(4) Fully diluting the lubricant with deionized water 10 times the mass of the lubricant respectively, adding the diluted lubricant into a second mixing container, and uniformly stirring;
(5) And adding the silane coupling agent solution in the first mixing container into a second mixing container, uniformly stirring, adding the rest deionized water, and adjusting the pH value to 5-7 to obtain a finished impregnating compound.
Examples of the experiments
1. Routine index test
The glass fiber sizing agents provided in the examples and comparative examples were applied to the preparation of 1000tex PA6T composite, wherein the glass fiber content was 40wt%. The specific source of the glass fiber is HS4 high-strength glass fiber self-made by the medium material technology. The glass fiber strands are dried by the oven before being processed in the subsequent process, so that the bundling property of the strands is improved, and the wear resistance of the yarns can be improved. The drying temperature of the protofilament is divided into three stages, namely 90 ℃ and 90min; at 105 ℃ for 180min; at 125 ℃ for 180min. The product is tested for various performance indexes, and the specific test method is as follows:
(1) Combustible content: reinforced article test method according to GB/T9914.2 part 2: and (4) measuring the combustible content of the glass fiber.
(2) Dry yarn tensile strength: according to GB/T7690.3 reinforcing material yarn test method part 3: determination of breaking strength and breaking elongation of glass fiber.
(3) Amount of hairiness: the method comprises the steps that all hairline weights generated by the twistless roving and a wear-resistant device in the friction period are in milligrams, the twistless roving and the wear-resistant device are rubbed by adopting multiple points, multiple friction materials and multiple friction angles, a sample is damaged at a constant winding speed, and the amount of collected hairline is measured after the process is finished; see figure 2 for a specific test setup.
(4) The method for testing the stiffness comprises the following steps: the stiffness test of the untwisted roving is carried out by adopting the national standard GB/T7690.4-2001.
(5) The roving was laid horizontally on a support with a spacing of 10m, and a certain degree of tension (0.098N/Tex) was applied, referring to GB18369, appendix B, and the difference between the maximum and minimum drapability of the glass fiber strand was taken as the drapability of the roving, which is called the natural draping height when the tension was 0.
(6) And (4) testing the bending property of the composite material according to a national standard GB/T1449-2005 fiber reinforced plastic bending property test method.
(7) And testing the tensile property of the composite material according to the tensile property testing method of the national standard GB/T1447-2005 fiber reinforced plastic.
(8) And testing the impact performance of the composite material according to a national standard GB/T1451-2005 fiber reinforced plastic simply supported beam type impact toughness test method.
TABLE 2 Dry glass fiber Properties
Dry yarn strength: characterizing the mechanical property of the glass fiber; stiffness: the soft and hard of the yarn is characterized, and the higher the yarn is, the harder the yarn is; feather: representing the roughness degree of the surface of the yarn, wherein the higher the roughness degree is, the more rough the surface of the yarn is; the suspension degree: the degree of yarn unraveling is characterized, the higher the raveless.
The performance of the glass fiber dry yarn is mainly influenced by the film forming agent and the lubricant, wherein the film forming agent mainly has the function of forming a layer of compact film on the surface of the glass fiber, repairing microcracks on the surface of the glass fiber, and improving the strength of the glass fiber and the bonding degree of the glass fiber and the resin. Example 2 the yarn was stiff and had more hairiness due to the excess of high molecular weight film former. Example 4 results in the yarn being hairy and having high hairiness due to too little lubricant, and example 5 results in the yarn being loose and having high drapability due to too much lubricant, but all can meet the requirements of normal use. Comparative examples 1-4 because the type and proportion of the formula of the film forming agent are out of the scope of the claims of the invention, the film with continuous and smooth performance on the surface of the glass fiber is not available, so that the tensile strength of the yarn is lower, and meanwhile, the comparative example 1 has over-hard yarn and high hairiness because of lack of the water-based polyamide emulsion; the comparative example 2 is that the yarn is too soft and the drapability is increased due to the lack of the high-molecular film forming agent, and the comparative example 3 is that the yarn is too hard and the hairiness is much due to the lack of the low-molecular film forming agent; comparative example 4 lack of high molecular film former can cause the yarn to be too soft, the mechanical property is reduced, and the drapability is increased; some of the properties of comparative examples 1-4 have not been satisfactory for conventional use. Comparative example 5 has little effect on the dry fiber glass properties, but has a greater effect on the properties of the composite.
TABLE 3 composite Properties
Note: the self-made non-thermoplastic aircraft yarn is a medium material science and technology product SC-1200BG7 (6) aircraft yarn, and the commercially available yarn is a Thai glass certain grade thermoplastic yarn with the same specification.
From the data in the table, the performance of the yarn overall composite material prepared by the impregnating compound formula provided by the invention is greatly improved compared with the existing product. The film forming agent of the impregnating compound main body is made of high-temperature resistant components, so that carbon residue caused by the fact that the impregnating compound is not resistant to high temperature in the composite material processing process is effectively prevented; meanwhile, the addition of the water-based polyamide emulsion greatly improves the mechanical properties of the contact of the resin and the fibers, particularly the bending properties representing the interface bonding capability, the bending modulus is more than 18GPa, the bending strength is more than 320MPa, which is far higher than that of a comparative example, and the influence of the lubricant on the interface bonding is reduced to the maximum extent while the fiber processing performance is ensured. The coupling agent is selected from a specific combination proportion, and the combination of the resin and the fiber is strengthened to the maximum extent in the high-temperature combination process.
2. High temperature resistance test
The products of the embodiment and the comparative example are prepared into composite material granules after being pre-melted at high temperature (330 ℃ for 3 min) by a double-screw extruder and granulated, and are injection molded into sample strips after being melted at high temperature (330 ℃ C.) by an injection molding machine. The glass fiber needs to be pre-mixed at high temperature in the processing process, for example, part of components in the impregnating compound have poor temperature resistance, and can be decomposed and generate carbon residue in the process, so that the color of the yarn surface and the composite material is darkened, and the appearance of the composite material are influenced.
Fig. 1 is a picture of a composite material sample strip after high-temperature injection molding, wherein the sample strip is a non-thermoplastic yarn (self-made) sample strip, a thermoplastic yarn (commercially available) sample strip suitable for common thermoplastic resin and a yarn sample strip prepared by using the treating compound in example 1, and the glass fiber contents of the three sample strips are all 30%. As can be seen from the figure, the product provided by the embodiment 1 of the invention has the lightest color and better high-temperature resistance after high-temperature injection molding. The pictures of the other embodiments are similar to embodiment 1 and are not shown one by one.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The glass fiber impregnating compound is characterized by comprising the following components in percentage by mass:
3-8% of film forming agent, 0.5-1.5% of lubricant and 0.5-1.2% of coupling agent;
wherein the film-forming agent comprises 2-4% of low molecular weight aqueous polyurethane with the number average molecular weight of 400-1500 and 0.5-2% of high molecular weight aqueous polyurethane with the number average molecular weight of 2000-4000, based on the total mass of the glass fiber sizing agent; 0.5-2% of water-based polyamide emulsion;
the coupling agent is a mixture of a silane coupling agent containing a benzene ring and a silane coupling agent containing amino and/or epoxy functional groups.
2. The glass fiber sizing agent according to claim 1, wherein said lubricant comprises 0.5-1.2% by mass of a non-ionic lubricant, based on the total mass of the glass fiber sizing agent; 0.1-0.3% of ionic lubricant.
3. The glass fiber sizing agent as claimed in claim 2, wherein said non-ionic lubricant is at least one of a mineral oil type lubricant, an ester type lubricant, a long-chain flexible benzene ring type lubricant, a silicone type lubricant or an amide type lubricant;
and/or the ionic lubricant is at least one of lubricant 6760L and lubricant 8760.
4. The glass fiber sizing agent according to claim 1, wherein the coupling agent is a silane coupling agent having a thermal decomposition temperature of 300 ℃ or higher;
optionally, the coupling agent comprises 0.4-0.8% of silane coupling agent containing benzene ring and 0.1-0.4% of silane coupling agent containing amino and/or epoxy functional group based on the total mass of the glass fiber sizing agent.
5. A glass fiber sizing composition according to any one of claims 1-4, characterized in that the total solid content of said glass fiber sizing composition is 5-6wt%;
and/or the pH value of the glass fiber impregnating compound is 5-7.
6. The glass fiber sizing agent according to claim 5, wherein a pH adjusting agent is used to adjust the pH of the glass fiber sizing agent;
optionally, the pH adjuster is an organic acid;
optionally, the organic acid is at least one of acetic acid, formic acid, succinic acid or citric acid.
7. A glass fiber sizing composition according to claim 5, wherein the balance is water.
8. A method for preparing a glass fiber sizing agent according to any one of claims 1 to 7, characterized by comprising the steps of:
s1, dispersing a coupling agent into water, and adjusting the pH value to obtain a coupling agent solution;
s2, mixing a film forming agent and a lubricant, mixing with the coupling agent solution, and adjusting the pH value to obtain the glass fiber impregnating compound;
optionally, the amount of water used in the step S1 is 4-6 times of the mass of the coupling agent;
optionally, the pH is adjusted to 5-7 in both steps S1 and S2.
9. Use of a glass fibre sizing composition according to any one of claims 1 to 7 for the manufacture of a thermoplastic high temperature resistant composite material.
10. The use according to claim 9, wherein the thermoplastic high temperature resistant composite is a composite of glass fibers and a matrix resin, the matrix resin being a PA6 resin;
optionally, the PA6 resin is PA6T resin.
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