CN117024006A - Impregnating compound for glass fibers and preparation method, product and application thereof - Google Patents
Impregnating compound for glass fibers and preparation method, product and application thereof Download PDFInfo
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- CN117024006A CN117024006A CN202311055247.9A CN202311055247A CN117024006A CN 117024006 A CN117024006 A CN 117024006A CN 202311055247 A CN202311055247 A CN 202311055247A CN 117024006 A CN117024006 A CN 117024006A
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- coupling agent
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- silane coupling
- sizing
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 73
- 150000001875 compounds Chemical class 0.000 title claims description 53
- 238000002360 preparation method Methods 0.000 title description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 96
- 239000000839 emulsion Substances 0.000 claims abstract description 84
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 81
- 238000004513 sizing Methods 0.000 claims abstract description 58
- 239000007787 solid Substances 0.000 claims abstract description 45
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004814 polyurethane Substances 0.000 claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 claims abstract description 42
- FRIIZRXZZDBOBW-UHFFFAOYSA-N methyl(prop-1-enyl)silane Chemical compound C[SiH2]C=CC FRIIZRXZZDBOBW-UHFFFAOYSA-N 0.000 claims abstract description 38
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000007822 coupling agent Substances 0.000 claims abstract description 34
- 239000004412 Bulk moulding compound Substances 0.000 claims abstract description 26
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- YMDCAYHEWFKCFR-UHFFFAOYSA-N 1-hydroxy-1-oxidopiperidin-1-ium Chemical compound O[N+]1([O-])CCCCC1 YMDCAYHEWFKCFR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 5
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- -1 (methyl) propyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The application discloses a sizing agent for glass fibers, which comprises effective components and water, wherein the solid content of the sizing agent is 7.61-18.3%, and the solid mass of each effective component in the sizing agent is expressed as follows: silane coupling agent 0.4-1.2%, film forming agent 7-16%, polymerization inhibitor 0.01-0.1%, pH regulator 0.2-1%. The silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, and the film forming agent is a mixture of a crosslinkable polyurethane emulsion and an unsaturated polyester emulsion. The glass fiber chopped strand product produced by coating with the sizing agent has good bundling property and fluidity, and the reinforced bulk molding compound product has high mechanical property, thereby meeting the demands of markets and applications.
Description
Technical Field
The application relates to the technical field of glass fiber production, in particular to a sizing agent for glass fibers, a preparation method, a product and application of the sizing agent, and is especially suitable for production of glass fiber reinforced bulk molding compound products.
Background
Bulk molding compound articles are prepared from unsaturated polyester resins, fillers, chopped glass fibers, and various additives by thoroughly mixing to form a bulk intermediate material, which is molded or injection molded. The bulk molding compound product has the advantages of low cost, good dimensional stability, heat resistance, good electrical property and the like, and is widely applied to the fields of mechanical manufacture, chemical equipment, buildings and the like.
The impregnating compound used for producing the chopped glass fibers for reinforcing bulk molding compound products at present is commonly used as a main film forming agent of cross-linked polyvinyl acetate emulsion. The sizing agent meets the production requirement of glass fibers to a certain extent, but the bundling property of the glass fibers produced by coating is too poor, meanwhile, the compatibility of the sizing agent with unsaturated polyester is not high, the interface bonding strength of the glass fibers and the unsaturated polyester is low, and the mechanical strength of the bulk molding compound product is low. Therefore, in order to improve the mechanical strength of bulk molding compound products, it is important to develop a glass fiber impregnating compound with high compatibility with unsaturated polyester.
Disclosure of Invention
In order to solve the technical problems, the application provides the impregnating compound for the glass fibers, and the glass fiber chopped strand product produced by coating the impregnating compound has good bundling property and fluidity, and the reinforced bulk molding compound product has high mechanical property and meets the demands of markets and applications.
In order to achieve the above purpose, the present application is realized by the following technical scheme:
according to one aspect of the present application, there is provided a sizing for glass fibers, the sizing comprising an effective component and water; the solid content of the impregnating compound is 7.61-18.3%, the effective components comprise a silane coupling agent, a film forming agent, a polymerization inhibitor and a pH value regulator, and the solid mass of each effective component of the impregnating compound is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, and the film forming agent is a mixture of a crosslinkable polyurethane emulsion and an unsaturated polyester emulsion.
Further, the solid content of the impregnating compound is 11.05-18.3%; the solid mass of each effective component of the impregnating compound is expressed as follows:
further, the aminosilane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane; the (methyl) propenyl silane coupling agent is gamma- (methacryloxy) propyl trimethoxy silane and/or gamma- (acryloxy) propyl trimethoxy silane.
Further, the mass ratio of the aminosilane coupling agent to the (methyl) propenyl silane coupling agent is 1:2-1:1.
Further, the crosslinkable polyurethane emulsion is nonionic, the polymer chain segment contains carbon-carbon double bonds, and the weight average molecular weight is smaller than 20000.
Further, the unsaturated polyester emulsion is nonionic, and the weight average molecular weight is less than 15000.
Further, the mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is 1:7-1:1.
Further, the polymerization inhibitor is at least one of sodium sulfate, diethyl hydroxylamine and piperidinol oxide.
Further, the pH regulator is at least one of acetic acid, oxalic acid and citric acid.
In the sizing agent for glass fibers, the amino group in the amino silane coupling agent has strong polarity, and the crosslinkable polyurethane emulsion has good cohesiveness to the glass fibers, so that the stiffness and the bundling property of the glass fibers can be improved. In the (methyl) propenyl silane coupling agent, the (methyl) propyl group can provide a crosslinking point, the unsaturated polyester emulsion has high carbon-carbon double bond content and strong reactivity, and the two can generate high crosslinking with the unsaturated polyester, so that the mechanical strength of the bulk molding compound product is improved. The polymerization inhibitor prevents the content of the carbon-carbon double bond in the silane coupling agent and the film forming agent from becoming low due to thermal initiation in the glass fiber production process. The pH adjustor facilitates the hydrolysis of the (meth) acryl silane coupling agent. Through the synergistic effect of the components in the impregnating compound, the glass fiber has better stiffness and cluster property, and the reinforced bulk molding compound product has high mechanical property and meets the demands of markets and applications.
The effect and the content of each effective component in the sizing agent for the glass fiber are described as follows:
the silane coupling agent can perform condensation reaction with the surface of the glass fiber and is firmly fixed on the surface of the glass fiber. The silane coupling agent of the application is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent. The amino silane coupling agent end group is amino group, has strong polarity, can form stronger intermolecular force with the film forming agent, and improves the bundling property of glass fibers. The (methyl) propenyl silane coupling agent terminal group is a (methyl) allyl group, has reactivity, can react with a film forming agent and unsaturated polyester resin, and improves the mechanical strength of bulk molding compound products. The aminosilane coupling agent of the application can be at least one of gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane. Wherein, the (methyl) propenyl silane coupling agent of the application can be gamma- (methacryloxy) propyl trimethoxy silane or/and gamma- (acryloxy) propyl trimethoxy silane. The amount of silane coupling agent must be controlled within a certain range: if the content of the silane coupling agent is too small, the interfacial bonding force between the glass fiber and the impregnating compound is poor; too much content results in less dispersion of the glass fibers. Therefore, the solid mass of the silane coupling agent is controlled to be 0.4-1.2 percent of the total mass of the impregnating compound; preferably 0.6 to 1.2%.
In the application, the relation of the dosage of the two silane coupling agents can be reasonably controlled, and the bundling property and stiffness of glass fibers and the mechanical property of bulk molding compound products can be reasonably adjusted and improved. The inventors have found that when the proportion of the aminosilane coupling agent is too low, the bundling property and stiffness of the glass fiber are deteriorated, and when the proportion of the (meth) acryl-based silane coupling agent is too low, the mechanical strength of the bulk molding compound product is lowered. Therefore, in the application, the mass ratio of the aminosilane coupling agent to the (methyl) propenyl silane coupling agent is controlled to be 1:2-1:1; exemplary mass ratio of aminosilane coupling agent to (meth) acryl silane coupling agent is 1:2, 1:1.7, 1:1.5, 1:1.2, 1:1.
The film forming agent is a main component of the sizing agent for the glass fiber, has the functions of protecting the glass fiber and improving the bundling property and stiffness of the glass fiber, and has decisive influence on the continuous production and application of the glass fiber. The film forming agent of the application adopts a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion. The crosslinkable polyurethane emulsion has strong polarity, can improve the bundling property and stiffness of glass fiber, and has reactivity; the unsaturated polyester emulsion has high carbon-carbon double bond content and strong reactivity, can be highly crosslinked with (methyl) propenyl silane coupling agent and unsaturated resin, and improves the mechanical strength of bulk molding compound products. The crosslinkable polyurethane emulsion of the application can be nonionic, the polymer chain segment contains carbon-carbon double bonds, and the weight average molecular weight is smaller than 20000, namely, the polyurethane synthesis formula contains hydroxyethyl acrylate or hydroxyethyl methacrylate monomers. Wherein, the unsaturated polyester emulsion of the application can be nonionic, and the weight average molecular weight is less than 15000. Meanwhile, the dosage of the film forming agent must be controlled within a certain range: the content of the film forming agent is too small, and the bundling property of glass fibers is too poor; if the content is too high, the effect of impregnating the unsaturated polyester with the glass fibers will be poor, and the glass fibers will not be impregnated completely. Therefore, the solid mass of the film forming agent is controlled to be 7-16% of the total mass of the impregnating compound; preferably 10 to 16%.
In the application, the relation of the dosage of the two film forming agents can be reasonably controlled, and the bundling property and stiffness of glass fibers and the mechanical property of bulk molding compound products can be reasonably adjusted and improved. The inventors have found that when the proportion of the crosslinkable polyurethane emulsion is too low, the bundling property and stiffness of the glass fiber become poor; when the proportion of the unsaturated polyester emulsion is too low, the mechanical strength of the bulk molding compound product becomes low. Therefore, the mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is controlled to be 1:7-1:1; exemplary mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1.
In the application, the polymerization inhibitor has the function of preventing the carbon-carbon double bonds in the (methyl) propenyl silane coupling agent, the crosslinkable polyurethane emulsion and the unsaturated polyester emulsion from generating thermal initiation when the precursor is dried at high temperature, the content of the carbon-carbon double bonds in the sizing agent is rapidly reduced by the thermal initiation, the crosslinking density of the sizing agent and the unsaturated polyester is finally reduced, and the mechanical property of the bulk molding compound product is reduced. The amount of polymerization inhibitor must be controlled within a certain range: the content of the polymerization inhibitor is too low, and the mechanical property of the bulk molding compound product is low; too much can lead to reduced initiator initiation efficiency during molding or injection molding of the dough-like intermediate material and to reduced mechanical properties of the dough-like molded article. Therefore, the solid mass of the polymerization inhibitor is controlled to be 0.01 to 0.1 percent of the total mass of the impregnating compound; preferably 0.05 to 0.1%.
The pH regulator is mainly used for promoting the hydrolysis of the (methyl) propenyl silane coupling agent in water. The pH regulator of the present application is preferably at least one acid selected from acetic acid, oxalic acid and citric acid. Illustratively, the pH adjustor is acetic acid. Acetic acid, oxalic acid and citric acid all can accelerate the hydrolysis of the (methyl) propenyl silane coupling agent in water. Meanwhile, the dosage of the pH value regulator must be controlled within a certain range: too little pH regulator content can cause too long hydrolysis time of the (methyl) propenyl silane coupling agent; too much content can result in too strong acidity of the system and reduced stability of the impregnating compound. Therefore, the solid mass of the pH value regulator is controlled to be 0.2-1% of the total mass of the impregnating compound; preferably 0.4 to 1%.
The application uses water as the disperse phase of each component of the impregnating compound, and compared with the solvent disperse phase, the water is more environment-friendly and safer. Wherein, the water is preferably deionized water.
The solid content of the impregnating compound is 7.61-18.3%, preferably 11.05-18.3%.
According to a second aspect of the present application, there is provided a method for preparing the sizing agent for glass fibers, comprising the steps of:
s1: adding water accounting for 20-40% of the total mass of the impregnating compound into a container, sequentially adding a pH value regulator and a silane coupling agent, and uniformly stirring;
s2: adding a film forming agent diluted by water into a container in the step S1;
s3: adding a polymerization inhibitor diluted by water into a container in the step S2;
s4: and (3) supplementing water to the impregnating compound mass set value in the container in the step (S3), and uniformly stirring.
Further, in the step S2, the film forming agent is diluted by water with the solid mass of 1-5 times.
Further, in the step S3, the polymerization inhibitor is diluted by water with the solid mass of 1-5 times.
The sequence of the step S2 and the step S3 is not fixed, and the sequence can be adjusted, namely, the film forming agent diluted by water is firstly added into the container of the step S1, and then the polymerization inhibitor diluted by water is added; the polymerization inhibitor diluted with water may be added to the container in the step S1, and then the film forming agent diluted with water may be added to the container in the step S1, or the film forming agent diluted with water and the polymerization inhibitor diluted with water may be added to the container in the step S1.
According to a third aspect of the present application, there is provided a glass fiber product produced from the foregoing glass fiber coated with a sizing agent.
According to a fourth aspect of the present application there is provided the use of the aforementioned glass fibre product in the field of reinforced dough moulded plastics articles.
The combustible content of the glass fiber is generally controlled to be 1.0-2.5%, and the combustible content is specifically required to be adjusted according to the performance index required to be achieved by the product.
Compared with the prior art, the glass fiber chopped strand product produced by coating with the sizing agent has good bundling property and fluidity, and the reinforced bulk molding compound product has high mechanical property, thereby meeting the demands of markets and applications.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the present application will be clearly and completely described in conjunction with the specific embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be arbitrarily combined with each other.
In the sizing agent for glass fibers of the present application, the advantageous effects of selecting the above-described ranges of the contents of the respective components will be illustrated by giving specific experimental data by way of examples.
The following are examples of preferred ranges of values for the components included in the sizing agent for glass fibers according to the present application.
Preferred examples one
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 7.61-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion, and the polymerization inhibitor is at least one of sodium sulfate, diethyl hydroxylamine and piperidinol oxide.
Preferred example two
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 7.61-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion, the aminosilane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, and the (methyl) propenyl silane coupling agent is gamma- (methacryloyloxy) propyltrimethoxysilane and/or gamma- (acryloyloxy) propyltrimethoxysilane.
Preferred examples three
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 7.61-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an amino silane coupling agent and a (methyl) propenyl silane coupling agent, and the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion; the crosslinkable polyurethane emulsion is nonionic, the polymer chain segment contains carbon-carbon double bonds, and the weight average molecular weight is less than 20000; the unsaturated polyester emulsion is nonionic, and the weight average molecular weight is less than 15000.
Preferred example four
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 7.61-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of a crosslinkable polyurethane emulsion and an unsaturated polyester emulsion, the mass ratio of the aminosilane coupling agent to the methyl propenyl silane coupling agent is 1:2-1:1, and the mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is 1:7-1:1.
Preferred example five
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 7.61-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion, and the mass ratio of the aminosilane coupling agent to the (methyl) propenyl silane coupling agent is 1:2-1:1; the aminosilane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane; the (methyl) propenyl silane coupling agent is gamma- (methacryloxy) propyl trimethoxy silane and/or gamma- (acryloxy) propyl trimethoxy silane.
Preferred example six
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 7.61-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of a crosslinkable polyurethane emulsion and an unsaturated polyester emulsion, and the mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is 1:7-1:1; the crosslinkable polyurethane emulsion is nonionic, the polymer chain segment contains carbon-carbon double bonds, and the weight average molecular weight is less than 20000; the unsaturated polyester emulsion is nonionic, and the weight average molecular weight is less than 15000.
Preferred examples seven
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 7.61-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion, and the mass ratio of the aminosilane coupling agent to the (methyl) propenyl silane coupling agent is 1:2-1:1; the aminosilane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane; the (methyl) propenyl silane coupling agent is gamma- (methacryloxy) propyl trimethoxy silane and/or gamma- (acryloxy) propyl trimethoxy silane; the mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is 1:7-1:1; the crosslinkable polyurethane emulsion is nonionic, the polymer chain segment contains carbon-carbon double bonds, and the weight average molecular weight is less than 20000; the unsaturated polyester emulsion is nonionic, and the weight average molecular weight is less than 15000; the polymerization inhibitor is at least one of sodium sulfate, diethyl hydroxylamine and piperidinol oxide.
Preferred example eight
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 11.05-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the mass ratio of the aminosilane coupling agent to the methyl propenyl silane coupling agent is 1:2-1:1, the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion, and the mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is 1:7-1:1.
Preferred example nine
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 11.05-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion, the aminosilane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, and the (methyl) propenyl silane coupling agent is gamma- (methacryloyloxy) propyltrimethoxysilane and/or gamma- (acryloyloxy) propyltrimethoxysilane.
Preferred examples ten
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 11.05-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an amino silane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of a crosslinkable polyurethane emulsion and an unsaturated polyester emulsion, the crosslinkable polyurethane emulsion is nonionic, the polymer chain segment contains carbon-carbon double bonds, and the weight average molecular weight is less than 20000; the unsaturated polyester emulsion is nonionic, and the weight average molecular weight is less than 15000.
Preferred example eleven
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 11.05-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion, and the mass ratio of the aminosilane coupling agent to the (methyl) propenyl silane coupling agent is 1:2-1:1; the aminosilane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane; the (methyl) propenyl silane coupling agent is gamma- (methacryloxy) propyl trimethoxy silane and/or gamma- (acryloxy) propyl trimethoxy silane; the mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is 1:7-1:1; the crosslinkable polyurethane emulsion is nonionic, the polymer chain segment contains carbon-carbon double bonds, and the weight average molecular weight is less than 20000; the unsaturated polyester emulsion is nonionic, and the weight average molecular weight is less than 15000.
Preferred example twelve
The sizing agent for glass fibers according to the present application comprises an effective component and water; the solid content of the impregnating compound is 11.05-18.3%; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, the film forming agent is a mixture of crosslinkable polyurethane emulsion and unsaturated polyester emulsion, and the polymerization inhibitor is at least one of sodium sulfate, diethyl hydroxylamine and piperidinol oxide. The preparation method of the sizing agent for glass fibers of the preferred examples one to twelve comprises the following steps:
s1: adding water accounting for 20-40% of the total mass of the impregnating compound into a container, sequentially adding a pH value regulator and a silane coupling agent, and uniformly stirring;
s2: adding a film forming agent diluted by water with the mass 1-5 times of the solid mass of the film forming agent into a container in the step S1;
s3: adding a polymerization inhibitor diluted by water with the mass 1-5 times of the solid mass of the polymerization inhibitor into a container in the step S2;
s4: and (3) supplementing water to the set value of the mass of the impregnating compound in the container in the step (S3), and fully stirring for 10-30 minutes to obtain the product.
The specific formulation of some examples of the sizing agent for glass fibers of the present application is shown in table 1, and the values in table 1 are the percentages of the solid mass of the effective components to the total mass of the sizing agent.
It should be noted that the specific types and amounts and combinations of the components selected in table 1 do not limit the scope of the present application.
The proportions of the effective components of the impregnating compounds in Table 1
Table 1 (subsequent)
In the embodiments 1 to 12 of the present application, the crosslinkable polyurethane emulsion is nonionic, the polymer chain segment contains carbon-carbon double bonds, and the weight average molecular weight is less than 20000; the unsaturated polyester emulsion is nonionic, and the weight average molecular weight is less than 15000.
To further illustrate the beneficial effects of the present application, two glass fiber sizing agents currently in common use were selected as comparative examples, namely comparative examples 1-2. The formulations of comparative examples 1 to 2 are shown below, wherein the amount of the effective components is the percentage of the solid mass of the effective components to the total mass of the impregnating compound.
Comparative example 1
Silane coupling agent 1: 0.5% of (meth) acryl silane coupling agent;
silane coupling agent 2: 0.1% of ureido silane coupling agent;
film forming agent 1: 8% of polyurethane emulsion;
film forming agent 2: 7% of epoxy resin emulsion;
pH regulator: acetic acid 0.3%;
water: 84.1%.
Comparative example 2
Silane coupling agent: 1% of an aminosilane coupling agent;
film forming agent 1: 3.3% of polyvinyl acetate emulsion;
film forming agent 2: 3.3% of polyurethane emulsion;
film forming agent 3: 3.3% of epoxy resin emulsion;
pH regulator: citric acid 0.3%;
water: 88.8%.
The prepared sizing agents (examples 1 to 12 and comparative examples 1 to 2) were applied to glass fibers having a fiber diameter of 13. Mu.m, and the drying process was hot air drying for 12 hours, and the chopped length of the final glass chopped strands was 6mm. The glass fiber, the unsaturated resin, the low shrinkage agent, the filler, the internal mold release agent, the curing agent and the carbon black are respectively prepared into bulk intermediate materials according to the proportion of 18:15.93:10.6:54:0.33:0.27:0.87, the bulk intermediate materials are molded into bulk molding compound products, and the bulk molding compound products and the glass fiber are tested, wherein the test results are shown in Table 2.
Table 2 results of performance testing of examples and comparative examples
Table 2 (subsequent)
As can be seen from the test results of bulk molding compound products in Table 2, the mechanical properties of the bulk molding compound products coated with the sizing agent of the present application (examples 1 to 12) were significantly improved over those of the glass fiber-reinforced unsaturated polyester resin coated with the sizing agent of comparative examples 1 to 2. Meanwhile, the bulk molding compound product prepared in example 8 has the highest mechanical properties. In addition, the inventors have used other comparative example sizing agents in which the silane coupling agent used was not a mixture of an aminosilane coupling agent and a (meth) acryl silane coupling agent, the film-forming agent was not a mixture of a crosslinkable polyurethane emulsion and an unsaturated polyester emulsion, and the mechanical properties of the sizing agents of the other comparative examples were also significantly inferior to those of the sizing agents of examples 1 to 12.
In conclusion, the formula and the preparation process of the sizing agent for the glass fiber provided by the application are scientific and reasonable. The glass fiber chopped strand product produced by coating the sizing agent has good bundling property and fluidity, and the reinforced bulk molding compound product has high mechanical property and meets the demands of markets and applications.
The above embodiments are only for illustrating the technical solution of the present application, and are not limiting. Although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. The sizing agent for the glass fiber is characterized by comprising an effective component and water, wherein the solid content of the sizing agent is 7.61-18.3%, the effective component comprises a silane coupling agent, a film forming agent, a polymerization inhibitor and a pH value regulator, and the solid mass of each effective component of the sizing agent accounts for the total mass of the sizing agent and is expressed as follows:
the silane coupling agent is a mixture of an aminosilane coupling agent and a (methyl) propenyl silane coupling agent, and the film forming agent is a mixture of a crosslinkable polyurethane emulsion and an unsaturated polyester emulsion.
2. The sizing agent according to claim 1, wherein the solid content of the sizing agent is 11.05-18.3%, and the percentage of the solid mass of each effective component of the sizing agent to the total mass of the sizing agent is represented as follows:
3. the sizing of claim 1, wherein the aminosilane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane, and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane; the (methyl) propenyl silane coupling agent is gamma- (methacryloxy) propyl trimethoxy silane and/or gamma- (acryloxy) propyl trimethoxy silane.
4. The sizing agent according to claim 1, wherein a mass ratio of the aminosilane coupling agent to the (meth) acryl silane coupling agent is 1:2 to 1:1.
5. The sizing of claim 1, wherein the crosslinkable polyurethane emulsion is nonionic, the polymer segment comprises a carbon-carbon double bond, and the weight average molecular weight is less than 20000; the unsaturated polyester emulsion is nonionic, and the weight average molecular weight is less than 15000.
6. The sizing of claim 1, wherein the mass ratio of the crosslinkable polyurethane emulsion to the unsaturated polyester emulsion is from 1:7 to 1:1.
7. The sizing of claim 1, wherein the polymerization inhibitor is at least one of sodium sulfate, diethylhydroxylamine, and piperidinol oxide.
8. A method for preparing the sizing agent for glass fibers according to any one of claims 1 to 7, comprising the steps of:
s1: adding water accounting for 20-40% of the total mass of the impregnating compound into a container, sequentially adding a pH value regulator and a silane coupling agent, and uniformly stirring;
s2: adding a film forming agent diluted by water into a container in the step S1;
s3: adding a polymerization inhibitor diluted by water into a container in the step S2;
s4: and (3) supplementing water to a set value of the mass of the impregnating compound in the container in the step (S3), and uniformly stirring to obtain the impregnating compound.
9. A glass fiber product produced by coating the glass fiber treating compound according to any one of claims 1 to 7.
10. Use of a glass fiber product according to claim 9 in the field of glass fiber reinforced bulk molding compounds.
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