CN104947410B - Glass fibre reinforcement and surface modification method - Google Patents
Glass fibre reinforcement and surface modification method Download PDFInfo
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- CN104947410B CN104947410B CN201510298143.XA CN201510298143A CN104947410B CN 104947410 B CN104947410 B CN 104947410B CN 201510298143 A CN201510298143 A CN 201510298143A CN 104947410 B CN104947410 B CN 104947410B
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Abstract
The present invention discloses a glass fibre reinforcement and surface modification method in the material manufacturing field of the automotive upholstery. According to the method, firstly, a modified polyurethane waterborne emulsion is prepared. Secondly, a water-soluble polyester, the modified polyurethane waterborne emulsion, the gamma-propyl-trimethoxy-silane, the gamma-propyl tri-methoxy silane, the deionized water, an ammonium salt and a fatty acid amide are adopted as raw materials and are mixed up to prepare a dipping solution. After that, a continuous glass fiber mat is immersed in the dipping solution and is taken out of the dipping solution after being subjected to supersonic vibration and impregnation. The obtained continuous glass fiber mat is dried while being kept out of the sun, and then a reinforced and surface-modified continuous glass fiber mat. According to the invention, the gamma-propyl-trimethoxy-silane and the gamma-propyl tri-methoxy silane are adopted as coupling agents to react with polyurethane to generate a copolymer. In this way, the interface performance of the fiber mat with a resin matrix is improved. Products obtained through the above method can be used for manufacturing the automotive upholstery and automotive structural parts, which have the advantages of light weight, small thickness and low cost under the same intensity.
Description
Technical field
The present invention relates to a kind of composite and its manufacture method that can be used to manufacture automotive upholstery, more particularly to a kind of
The composite of glass fibre and polyurethane.
Background technology
Glass fibre continuous felt is a kind of new inorganic reinforcement, because excellent performance is widely used in electrical equipment, vapour
The industries such as car.Glass continuous strand felt isotropism, it is respectively higher to intensity, and bond strength between layers are high, voidage is high, because of its tool
Have resin impregnated speed fast and uniform advantage, and application in the automotive industry is more and more wider, be such as applied to manufacture inside gadget,
Structural member etc..It is disadvantageous in that：When this glass fibre continuous felt is used to manufacture automotive upholstery and structural member, with powder
The big shortcoming of dirt, can bring compared with major injury to the workman of long period of operation, easily suffer from pneumoconiosis.In addition, existing glass fibre connects
Continuous felt mechanical property also has the space for further being lifted, and remains at present weight weight, thickness is big, high cost shortcoming.
The content of the invention
It is an object of the invention to provide a kind of glass fiber reinforcement and surface modifying method so as to more preferable mechanics can be obtained
Performance.
The object of the present invention is achieved like this：A kind of glass fiber reinforcement and surface modifying method, comprise the steps：
1）Prepare modified polyurethane water-based emulsion：Hydroxy silicon oil is added in polyurethane, reaction is formed after block copolymer,
It is again that glycidyl ester epoxy resin is dispersed in the copolymer, it is eventually adding deionized water and is emulsified, it is modified
Polyurethane aqueous emulsions；In the raw material for preparing modified polyurethane water-based emulsion, the weight portion of each component is：Polyurethane 30, hydroxyl
Base silicone oil 2-5, glycidyl ester epoxy resin 1-3, deionized water 50-75；
2）Prepare dipping solution：By water-soluble polyester, modified polyurethane water-based emulsion, γ propyltrimethoxy silane, go
Ionized water, ammonium salt and fatty acid amide are weighed by weight mixing, are stirred, and adjust pH value for 3-6；Wherein, each component
Weight portion be：Water-soluble polyester 1, modified polyurethane water-based emulsion 3-8, γ propyltrimethoxy silane 0.06-3.05, ammonium
Salt 0.01-3, fatty acid amide 3-6, deionized water 60-84；
3）Immersion：Continuous Glass Fiber Mat is immersed in dipping solution；
4）Vibration：To be placed on ultrasonic vibration installation immersed with the container of continuous Glass Fiber Mat；
5）Open ultrasonic vibration installation to force dipping 5-10 minutes, the continuous Glass Fiber Mat of taking-up, lucifuge is dried, obtain
Strengthen and the modified continuous Glass Fiber Mat in surface.
In the present invention, the ammonium salt is the one kind in ammonium sulfate, ammonium carbonate, ammonium chloride, ammonium acetate, ammonium formate.
The step 2 of the present invention）Middle adjustment pH value is using the one kind in hydrochloric acid, sulfuric acid, acetic acid, formic acid.
γ propyltrimethoxy silane in the present invention is coupling agent, can form block copolymer with polyurethane, is helped
In the interface performance for improving fibrofelt and resin matrix.The modified polyurethane of Jing hydroxy silicon oils and glycidyl ester epoxy resin
Water-based emulsion, has the advantages that good, the flexible performance such as soft or hard controllability, film high resilience, adhesion strength are big, is a kind of excellent
Size film-forming components.Excellent protective effect is not only served to glass fibre, at the same with polyurethane matrix compound tense,
The interface binding power of reinforcing fiber mats and matrix is improved by chemical bonding, it is typically the aqueous of cation or nonionic
Polyaminoester emulsion.Ammonium salt is antistatic additive, forms conductive channel, it is possible to decrease charge buildup.Fatty acid amide is lubricant.Can drop
Low-friction coefficient.Continuous Glass Fiber Mat after process is used for polyurethane foam and strengthens composite materials testing, itself and polyurethane
It is firmly combined with, tensile strength is big, under equal conditions the bending modulus of composite improves more than 20%.The product that the method is obtained
Product can be used to manufacture automotive upholstery and structural member, have the advantages that the thickness under lightweight, equality strength is little, low cost.
Specific embodiment
Embodiment 1
A kind of glass fiber reinforcement and surface modifying method, are carried out as follows：
1）Prepare modified polyurethane water-based emulsion：
Hydroxy silicon oil is added in polyurethane, reaction is formed after block copolymer, then by glycidyl ester epoxy resin
It is dispersed to be eventually adding deionized water and emulsified in the copolymer, obtain modified polyurethane water-based emulsion；It is modified preparing
In the raw material of polyurethane aqueous emulsions, the weight portion of each component is：
Polyurethane 3kg
Hydroxy silicon oil 0.2kg
Glycidyl ester epoxy resin 0.1kg
Deionized water 5kg
The modified polyurethane water-based emulsion being prepared from is used as one of raw material of the invention.
2）Dipping solution is prepared：
Weigh by following weight portion：
Water-soluble polyester 1kg
Modified polyurethane water-based emulsion 3kg
γ propyltrimethoxy silane 0.06kg
Ammonium chloride 0.01kg
Fatty acid amide 3kg
Deionized water 60kg
Mix after weighing, stir, and adopt hydrochloric acid to adjust pH value for 3-6.
3）Immersion：Continuous Glass Fiber Mat is immersed in dipping solution.
4）Vibration：By step 3）It is placed on ultrasonic vibration installation immersed with the container of continuous Glass Fiber Mat；
5）Open ultrasonic vibration installation and force dipping 5 minutes, the continuous Glass Fiber Mat of taking-up, lucifuge is dried, and is increased
The strong and modified continuous Glass Fiber Mat in surface.
Continuous Glass Fiber Mat after process is used for polyurethane foam and strengthens composite materials testing, the combination of itself and polyurethane
Firmly, tensile strength is big, and under equal conditions the bending modulus of composite improves more than 20%.
Embodiment 2
A kind of glass fiber reinforcement and surface modifying method, are carried out as follows：
1）Prepare modified polyurethane water-based emulsion：
Hydroxy silicon oil is added in polyurethane, reaction is formed after block copolymer, then by glycidyl ester epoxy resin
It is dispersed to be eventually adding deionized water and emulsified in the copolymer, obtain modified polyurethane water-based emulsion；It is modified preparing
In the raw material of polyurethane aqueous emulsions, the weight portion of each component is：
Polyurethane 8kg
Hydroxy silicon oil 0.27kg
Glycidyl ester epoxy resin 0.8kg
Deionized water 20kg
The modified polyurethane water-based emulsion being prepared from is used as one of raw material of the invention.
2）Dipping solution is prepared：
Weigh by following weight portion：
Water-soluble polyester 1kg
Modified polyurethane water-based emulsion 8kg
γ propyltrimethoxy silane 3.05kg
Ammonium sulfate 3kg
Fatty acid amide 6kg
Deionized water 84kg
Mix after weighing, stir, and adopt dilute sulfuric acid to adjust pH value for 3-6.
3）Immersion：Continuous Glass Fiber Mat is immersed in dipping solution.
4）Vibration：By step 3）It is placed on ultrasonic vibration installation immersed with the container of continuous Glass Fiber Mat；
5）Open ultrasonic vibration installation and force dipping 10 minutes, the continuous Glass Fiber Mat of taking-up, lucifuge is dried, and is increased
The strong and modified continuous Glass Fiber Mat in surface.
Continuous Glass Fiber Mat after process is used for polyurethane foam and strengthens composite materials testing, the combination of itself and polyurethane
Firmly, tensile strength is big, and under equal conditions the bending modulus of composite improves more than 20%.
Embodiment 3
A kind of glass fiber reinforcement and surface modifying method, are carried out as follows：
1）Prepare modified polyurethane water-based emulsion：
Hydroxy silicon oil is added in polyurethane, reaction is formed after block copolymer, then by glycidyl ester epoxy resin
It is dispersed to be eventually adding deionized water and emulsified in the copolymer, obtain modified polyurethane water-based emulsion；It is modified preparing
In the raw material of polyurethane aqueous emulsions, the weight portion of each component is：
Polyurethane 30kg
Hydroxy silicon oil 4kg
Glycidyl ester epoxy resin 2kg
Deionized water 60kg
The modified polyurethane water-based emulsion being prepared from is used as one of raw material of the invention.
2）Dipping solution is prepared：
Weigh by following weight portion：
Water-soluble polyester 1kg
Modified polyurethane water-based emulsion 5kg
γ propyltrimethoxy silane 20.3kg
Ammonium acetate 1kg
Fatty acid amide 4kg
Deionized water 80kg
Mix after weighing, stir, and adopt hydrochloric acid to adjust pH value for 3-6.
3）Immersion：Continuous Glass Fiber Mat is immersed in dipping solution.
4）Vibration：By step 3）It is placed on ultrasonic vibration installation immersed with the container of continuous Glass Fiber Mat；
5）Open ultrasonic vibration installation and force dipping 8 minutes, the continuous Glass Fiber Mat of taking-up, lucifuge is dried, and is increased
The strong and modified continuous Glass Fiber Mat in surface.
Continuous Glass Fiber Mat after process is used for polyurethane foam and strengthens composite materials testing, the combination of itself and polyurethane
Firmly, tensile strength is big, and under equal conditions the bending modulus of composite improves more than 20%.
Embodiment 4
A kind of glass fiber reinforcement and surface modifying method, are carried out as follows：
1）Prepare modified polyurethane water-based emulsion：
Hydroxy silicon oil is added in polyurethane, reaction is formed after block copolymer, then by glycidyl ester epoxy resin
It is dispersed to be eventually adding deionized water and emulsified in the copolymer, obtain modified polyurethane water-based emulsion；It is modified preparing
In the raw material of polyurethane aqueous emulsions, the weight portion of each component is：
Polyurethane 30kg
Hydroxy silicon oil 3kg
Glycidyl ester epoxy resin 3kg
Deionized water 70kg
The modified polyurethane water-based emulsion being prepared from is used as one of raw material of the invention.
2）Dipping solution is prepared：
Weigh by following weight portion：
Water-soluble polyester 10kg
Modified polyurethane water-based emulsion 30kg
γ propyltrimethoxy silane 20.4kg
Ammonium formate 20kg
Fatty acid amide 35kg
Deionized water 600kg
Mix after weighing, stir, and adopt formic acid to adjust pH value for 3-6.
3）Immersion：Continuous Glass Fiber Mat is immersed in dipping solution.
4）Vibration：By step 3）It is placed on ultrasonic vibration installation immersed with the container of continuous Glass Fiber Mat；
5）Open ultrasonic vibration installation to force dipping 5-10 minutes, the continuous Glass Fiber Mat of taking-up, lucifuge is dried, obtain
Strengthen and the modified continuous Glass Fiber Mat in surface.
Continuous Glass Fiber Mat after process is used for polyurethane foam and strengthens composite materials testing, the combination of itself and polyurethane
Firmly, tensile strength is big, and under equal conditions the bending modulus of composite improves more than 20%.
Embodiment 5
A kind of glass fiber reinforcement and surface modifying method, are carried out as follows：
1）Prepare modified polyurethane water-based emulsion：
Hydroxy silicon oil is added in polyurethane, reaction is formed after block copolymer, then by glycidyl ester epoxy resin
It is dispersed to be eventually adding deionized water and emulsified in the copolymer, obtain modified polyurethane water-based emulsion；It is modified preparing
In the raw material of polyurethane aqueous emulsions, the weight portion of each component is：
Polyurethane 30kg
Hydroxy silicon oil 5kg
Glycidyl ester epoxy resin 3kg
Deionized water 50kg
The modified polyurethane water-based emulsion being prepared from is used as one of raw material of the invention.
2）Dipping solution is prepared：
Weigh by following weight portion：
Water-soluble polyester 10kg
Modified polyurethane water-based emulsion 45kg
γ propyltrimethoxy silane 0.8kg
Ammonium carbonate 15kg
Fatty acid amide 60kg
Deionized water 840kg
Mix after weighing, stir, and adopt acetic acid to adjust pH value for 3-6.
3）Immersion：Continuous Glass Fiber Mat is immersed in dipping solution.
4）Vibration：By step 3）It is placed on ultrasonic vibration installation immersed with the container of continuous Glass Fiber Mat；
5）Open ultrasonic vibration installation to force dipping 5-10 minutes, the continuous Glass Fiber Mat of taking-up, lucifuge is dried, obtain
Strengthen and the modified continuous Glass Fiber Mat in surface.
Above-described embodiment is the invention is not limited in, on the basis of technical scheme disclosed by the invention, the skill of this area
Art personnel are according to disclosed technology contents, it is not necessary to which performing creative labour just can make one to some of which technical characteristic
A little to replace and deform, these are replaced and deform within the scope of the present invention.
Claims (3)
1. a kind of glass fiber reinforcement and surface modifying method, it is characterised in that comprise the steps：
1）Prepare modified polyurethane water-based emulsion：Hydroxy silicon oil is added in polyurethane, reaction is formed after block copolymer, then will
Glycidyl ester epoxy resin is dispersed in the copolymer, is eventually adding deionized water and is emulsified, and obtains the poly- ammonia that is modified
Ester water-based emulsion；In the raw material for preparing modified polyurethane water-based emulsion, the weight portion of each component is：Polyurethane 30, hydroxyl silicon
Oily 2-5, glycidyl ester epoxy resin 1-3, deionized water 50-75；
2）Prepare dipping solution：By water-soluble polyester, modified polyurethane water-based emulsion, γ propyltrimethoxy silane, deionization
Water, ammonium salt and fatty acid amide are weighed by weight mixing, are stirred, and adjust pH value for 3-6；Wherein, the weight of each component
Measuring part is：Water-soluble polyester 1, modified polyurethane water-based emulsion 3-8, γ propyltrimethoxy silane 0.06-3.05, ammonium salt
0.01-3, fatty acid amide 3-6, deionized water 60-84；
3）Immersion：Continuous Glass Fiber Mat is immersed in dipping solution；
4）Vibration：To be placed on ultrasonic vibration installation immersed with the container of continuous Glass Fiber Mat；
5）Open ultrasonic vibration installation to force dipping 5-10 minutes, the continuous Glass Fiber Mat of taking-up, lucifuge is dried, and is strengthened
And the modified continuous Glass Fiber Mat in surface.
2. a kind of glass fiber reinforcement according to claim 1 and surface modifying method, it is characterised in that：The ammonium salt is
One kind in ammonium sulfate, ammonium carbonate, ammonium chloride, ammonium acetate, ammonium formate.
3. a kind of glass fiber reinforcement according to claim 1 and 2 and surface modifying method, it is characterised in that：Step 2）
Middle adjustment pH value is using the one kind in hydrochloric acid, sulfuric acid, acetic acid, formic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750111A (en) * | 2016-12-27 | 2017-05-31 | 安徽潜源教学设备有限公司 | A kind of polyurethane plastic runway of glass fiber reinforcement and preparation method thereof |
| CN109265823A (en) * | 2018-08-31 | 2019-01-25 | 合肥开捷汽车科技有限公司 | A kind of automobile buffer beam and preparation method thereof |
| CN109809106A (en) * | 2018-11-28 | 2019-05-28 | 青岛环球输送带有限公司 | A kind of dedicated heat resistance conveyor belt of large junk and its preparation process |
| CN109706745A (en) * | 2018-12-18 | 2019-05-03 | 四川省玻纤集团有限公司 | A kind of glass base fabric weaves coating processes online |
| CN109722006B (en) * | 2019-01-03 | 2021-07-27 | 菲洛姆(福建)新材料科技有限责任公司 | Polyurethane elastic material suitable for transmission part and preparation method thereof |
| CN109703119A (en) * | 2019-01-22 | 2019-05-03 | 重庆纤维研究设计院股份有限公司 | Waterborne polyurethane modified oil resistant abrasive glass fibers blanket and preparation method thereof |
| CN112811823A (en) * | 2021-01-28 | 2021-05-18 | 安徽吉曜玻璃微纤有限公司 | Super glass wool and production process thereof |
| CN113321907B (en) * | 2021-04-28 | 2022-08-09 | 张晓军 | Composite 3D printing material containing coffee grounds and preparation method and application thereof |
| CN115678253A (en) * | 2022-11-16 | 2023-02-03 | 黄河科技学院 | Polyurethane composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2864072B1 (en) * | 2003-12-17 | 2006-01-27 | Saint Gobain Vetrotex | ENSIMES GLASS YARNS FOR REINFORCING POLYMERIC MATERIALS, IN PARTICULAR BY MOLDING |
| CN101376571B (en) * | 2007-08-27 | 2011-04-27 | 江苏九鼎新材料股份有限公司 | Non-alkali enhanced treating compound for glass fibre |
| JP2009143765A (en) * | 2007-12-14 | 2009-07-02 | Nippon Electric Glass Co Ltd | Glass fiber sizing agent, glass fiber, method for producing the glass fiber and glass fiber reinforced thermoplastic resin |
| CN102092963A (en) * | 2009-12-10 | 2011-06-15 | 胥建中 | Reinforced impregnating agent for alkali-free glass fibers |
| CN102219399B (en) * | 2011-03-31 | 2012-11-14 | 山东玻纤复合材料有限公司 | Impregnating compound special for single-filament plastic coated yarn and preparation method thereof |
| CN104556740A (en) * | 2013-10-17 | 2015-04-29 | 江西大华云通玻纤有限公司 | Formula of impregnating compound for glass fiber twisted yarn for textile use |
| CN103880300B (en) * | 2014-01-29 | 2016-08-17 | 巨石集团有限公司 | A kind of size of thermoplastic glass's direct yarn of steel conduit alkali-free glass fibre |
| CN104497260B (en) * | 2014-12-26 | 2018-01-26 | 重庆国际复合材料有限公司 | A kind of polyaminoester emulsion, its preparation method and glass fiber infiltration agent |
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Effective date of registration: 20220817 Address after: No. 8, Huayuan Road, Gongdao Town, Yangzhou City, Jiangsu Province, 225000 Patentee after: Yangzhou Yangzi Daihe Composite Products Co.,Ltd. Address before: No. 3, Huayuan West Road, Gongdao Town, Hanjiang District, Yangzhou City, Jiangsu Province, 225000 Patentee before: YANGZHOU CITY HANJIANG YANGZI AUTOMOBILE INNER DECORATION PARTS Co.,Ltd. |
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