CN103183844A - Surface modification glass fiber and preparation method and application thereof - Google Patents
Surface modification glass fiber and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a surface modification glass fiber and a preparation method and an application thereof, and belongs to the fields of surface modification fibers and preparation thereof. The preparation method is characterized in that the copolymer solution is adopted to be coated on the surface of the pre-processed glass fiber, wherein the copolymer used in the method comprises dodecyl methacrylate, styrene, and maleic anhydride; and the glass fiber is pre-processed by a coupling agent KH550. The surface modification glass fiber, provided by the invention, has the advantages that the preparation process is simple; the cost is low; the industrialization is facilitated; the dispersing performance and the heat stability of the modification glass fiber are good after the preparation method; and the surface modification glass fiber can be well bonded with thermoplastic resin.
Description
Technical field
The invention belongs to surface modified fibre and preparation field thereof, particularly a kind of surface modification glass fibre and preparation method and application thereof.
Background technology
In fiber-reinforced resin matrix compound material, the bonding degree of fiber and basal body interface is the important symbol that determines its boundary strength.Therefore, improving the interfacial adhesion performance is one of key factor of composite material interface control techniques.Contacting and wet processes of fiber and matrix experienced in fiber and the formation of basal body interface layer usually.Since fiber in the substrate molecule with various groups or different to the adsorptive power of various components in the system, in the forming process of interface, the wetting or nonwetting magnetism size that depends on fiber and matrix or other component.Produce wetting phenomena, fiber always will adsorb the material that those can reduce its surface energy, especially preferentially adsorbed those can reduce the material of its surface energy significantly.It is to improve wetting between fiber and the resin on the one hand that fiberglass surfacing is carried out purpose that properties-correcting agent handles, is the stick intensity that improves the interface on the other hand.Glass fibre is the main strongthener of fiber-reinforced resin matrix compound material, it can with various resin-bonded, form multiple matrix material with excellent properties.But glass fibre is polar mineral matter, and when it and most of nonpolar thermoplastic resin compound tense, because the interface bonding is bad, the mechanical property of matrix material is relatively poor, presses for the surface property that improves glass fibre, can be well bonding with thermoplastic resin.In order to improve the interfacial adhesion between glass fibre and the resin, a lot of scholars have done big quantity research.Common method has: 1, with small molecules coupling agent treatment glass fibre; 2, handle glass fibre with the macromole segmented copolymer; 3, by the copolymer coated fiberglass surfacing that improves.
At present, small molecules coupling agent treatment glass fibre has been realized industrialization, adopts the treating compound prescription to handle glass fibre mostly.Calendar year 2001, Jieshijie Novel Materials Co., Ltd, Shanghai has applied for the patent (CN1386714) of fiberglass surface treating agent, this treatment agent comprises membrane-forming agent, coupling agent, emulsifying agent and solvent, the weight percent of each component is: membrane-forming agent 0.5%～1%, coupling agent 2.5%～3%, emulsifying agent 0.2%～0.8%, solvent 95.2%～96.8%, wherein membrane-forming agent is low polarity or apolar substance, coupling agent is silane coupling agent, emulsifying agent is the alkyl diphenyl ethers, and solvent is made up of non-polar solvent, weak polar solvent and water.In January, 2011, the Yellow River and Huai He River institute has applied for the patent (CN102173602A) of a kind of surface treated glass fibre, preparation method and application, this glass fibre makes through silane coupling agent processing and heavy metal chelant processing, method is that the glass fibre after silane coupling agent is handled is handled with heavy metal chelant, heavy metal chelant and silane coupling agent generation chemical reaction, realize bonding, make surface treated glass fibre.Surface energy, form and the surface active mechanism of glass fibre after silane coupling agent KH550, KH560, KH570 handle has been studied in easy Changhai etc., its as a result the fiberglass surfacing crossed of display process have active function groups to produce, and with fiberglass surfacing in conjunction with belonging to Chemical bond.Though these methods have changed the surface energy of glass fibre, but what all adopt is small-molecule substance, owing to do not contain active group on thermoplastic resin such as PP, the PS molecular chain, can not with conventional small molecules coupling agent treatment after glass fibre form good combination, be difficult to bring into play the reinforced effects of glass fibre.
Along with the development of atom transfer radical polymerization (ATRP) technology, preparation controlled block multipolymer becomes the emphasis of many scholar's research, and segmented copolymer can have the fiberglass surfacing that improves that the structure of setting can be best, improves the interface performance of matrix material.Zhou Xiaodong (functional polymer journal, 2004,17 (3): 417～420) synthesized vinylbenzene and divinyl and contain the block copolymerization coupling agent of the two key silane of C=C, adopt this segmented copolymer that glass fibre has been carried out surface treatment, its modified effect is better than common small molecules coupling agent, and after glass fibre and polypropylene were compound, its interface shear strength increased to 3.71MPa by 2.97MPa.Gao Yan (East China University of Science's journal, 2006,32 (10): 1201～1205) adopt the ATRP technology, synthesized triblock copolymer (PSTK) with vinylbenzene (St), methacrylic acid 14 esters (TMA) with 3～methacryloxypropyl trimethoxy silane (KH570), toluene solution with certain density this segmented copolymer soaks glass mat, and then toast to form firm chemical bond, and then be molded into sheet material.Found that: the mechanical property of PP/ glass fibre improves comprehensively, and its shock strength is by 5.49kJ/m
2Increase to 18.49kJ/m
2Gao Yan etc. think because the siloxanes in the macromolecular coupling agent can hydrolysis generate the silicon hydroxyl, can form stronger chemical bond or hydrogen bond with the hydroxyl reaction of fiberglass surfacing; On the other hand, obviously the alkyl chain in the macromolecular coupling agent can more effectively tangle with matrix resin, thereby makes the mechanics improved performance bigger.But the synthetic method ATRP of this segmented copolymer is strict with the reaction environment anhydrous and oxygen-free, so this method is difficult to realize industrialization.
Adopt copolymer coated method to handle the shortcoming that fiberglass surfacing can remedy above two class methods.
Summary of the invention
The purpose of this invention is to provide a kind of surface modification glass fibre and preparation method and application thereof, surface modification glass fibre of the present invention is to adopt the method for coating to handle fiberglass surfacing, make control and the optimization of interface structure between glass fibre and the matrix, both increased by two alternate interface combinations, also increased the deformability of interface under stress, thereby intensity, modulus and the toughness of matrix material can be improved simultaneously.
Surface modification glass fibre of the present invention is the film that covers one deck coupling agent KH550 on the glass fibre earlier, and then coating one deck copolymer film, the surface-modifying agent of surface modification glass fibre is multipolymer, the monomer of this multipolymer is methacrylic dodecyl gallate, vinylbenzene and maleic anhydride, and general structure is:
(this multipolymer is random copolymers n, m, the k value is uncertain)
Surface modification glass fibre of the present invention is earlier via coupling agent KH550 pre-treatment, by being applied by multipolymer.
The pre-treatment of surface modification glass fibre of the present invention is: get 1% aqueous ethanolic solution and KH550, preparation coupling agent KH550 solution, the volume ratio of 1% aqueous ethanolic solution and KH550 consumption is 50:1-100:1, mixing, add glass fibre, the glass fibre add-on is the 10-25% of 1% aqueous ethanolic solution and KH550 gross weight, takes out glass fibre, namely gets the pre-treatment glass fibre;
The KH550 that provides among the present invention is γ-An Bingjisanyiyangjiguiwan.
The surface-modifying agent polymer monomers is methacrylic dodecyl gallate, vinylbenzene, maleic anhydride, and its mol ratio is methacrylic dodecyl gallate, vinylbenzene, maleic anhydride: 1:1:1～3:2:2;
Its compound method is for getting fiberglass surfacing properties-correcting agent multipolymer, is formulated as weight ratio and is 1～5% tetrahydrofuran solution, after the pre-treatment glass fibre is immersed, takes out, and dries, and namely gets surface modification glass fibre of the present invention.
Surface modification glass fibre of the present invention is mainly used in strengthening composite polyolefine material, as polyethylene and polypropylene composite material.Along with developing rapidly of China's oil chemical industry, the production of polyethylene and acrylic resin and development are fast more than other plastics.Because the raw material sources of polyolefin resin are wide, relative density is little, price is low, Corrosion Protection and good electrical property, and certain physical strength is arranged, and to be applied in engineering, polypropylene and vinyon are after modified glass-fiber strengthens, performance improves a lot, and brings up to the engineering plastics level by general-purpose plastics.Reinforced polypropylene compound material particularly is because its good combination property develops very fast.
Surface modification glass fibre preparation method of the present invention is as follows:
(1) preparation of multipolymer: be raw material with methacrylic dodecyl gallate, vinylbenzene, maleic anhydride, the mol ratio of methacrylic dodecyl gallate, vinylbenzene, maleic anhydride is: 1:1:1～3:2:2, stir, and adding initiator, initiator is benzoyl peroxide or Diisopropyl azodicarboxylate, and the add-on of initiator is raw material gross weight 0.6～1.5%; Solvent is toluene or benzene, nitrogen protection, and temperature of reaction is 60～85 ℃, the reaction times is 6～10 hours, desolventizes and drying, obtains the surface-modifying agent multipolymer;
(2) pre-treatment of glass fibre: get 1% aqueous ethanolic solution and KH550(γ-An Bingjisanyiyangjiguiwan), preparation coupling agent KH550 solution, the volume ratio of 1% aqueous ethanolic solution and KH550 consumption is 50:1-100:1, mixes, after leaving standstill 10-20 minute, add glass fibre, the glass fibre add-on is the 10-25% of 1% aqueous ethanolic solution and KH550 gross weight, behind the immersion 0.2-2h, take out glass fibre, oven dry, standby, obtain the pre-treatment glass fibre;
(3) surface modification of glass fibre: the fiberglass surfacing properties-correcting agent multipolymer of getting preparation in the step (1), add tetrahydrofuran (THF), be formulated as weight ratio and be 1～5% tetrahydrofuran solution, the pre-treatment glass fibre that adds preparation in the step (2), soak 1～3h, take out glass fibre, dry, obtain the surface modification glass fibre.
The KH550 that provides among the present invention is γ-An Bingjisanyiyangjiguiwan.
The present invention at first handles fiberglass surfacing with the small molecules silane coupling agent that contains functional group, make itself and glass fibre form chemical bonding, the macromonomer copolymer that chemical bonding can take place with the functional group of silane coupling agent again is coated on pretreated fiberglass surfacing, so both formed chemical bonding, introduced the macromole alkyl chain again, and multipolymer can prepare with common radical polymerization, and is easy to implement.Its advantage is: adopting macromole properties-correcting agent is that its organic segment is longer on the one hand, can be combined with the macromolecular chain phase mutual diffusion of matrix and the effective interface of formation of tangling, thereby at two alternate introducing compliant interface layers, both increased by two alternate interface combinations, also increased the deformability of interface under stress, thereby intensity, modulus and the toughness of matrix material can be improved simultaneously.On the other hand, macromole properties-correcting agent is made up of multipolymer, the different components of multipolymer can play different effects in to the improvement at interface, therefore can be by changing molecular weight and the molecular structure of macromole properties-correcting agent, and then intensity and the modulus of regulating this properties-correcting agent, thereby realization is to control and the optimization of interface structure between glass fibre and the matrix.
Embodiment
Following examples is further explained content of the present invention, but not in order to limit the present invention.
Embodiment 1
The preparation of multipolymer: take by weighing 12.7g methacrylic dodecyl gallate, 5.2g vinylbenzene, 4.9g maleic anhydride respectively, the 0.1368g benzoyl peroxide is measured 25mL toluene, adds in the three-necked flask, fully stirs, and logical nitrogen is warming up to 60 ℃, reaction 6h.After reaction finishes, revolve to steam and remove toluene, use petroleum ether precipitation, suction filtration is put into vacuum drying oven with product, and drying namely got multipolymer in 8 hours;
The pre-treatment of glass fibre: get the 50mL1% aqueous ethanolic solution, measure 1mLKH550, in beaker, mix, leave standstill 20 minutes after, add the 6g glass fibre, soak 0.2h after, take out glass fibre, in stink cupboard, dry 70 ℃ of dry for standby; The surface modification of glass fibre: get multipolymer, add tetrahydrofuran (THF), being formulated as weight ratio is 1% tetrahydrofuran solution, add pretreated glass fibre, soak 1.5h, take out glass fibre, in stink cupboard, dry, place 70 ℃ of dry 3h of vacuum drying oven, the gained glass fibre can be well compound with polypropylene.
Embodiment 2
The preparation of multipolymer: take by weighing 25.4g methacrylic dodecyl gallate, 10.4g vinylbenzene, 4.9g maleic anhydride respectively, the 0.3256g Diisopropyl azodicarboxylate is measured 35mL toluene, adds in the three-necked flask, fully stirs, and logical nitrogen is warming up to 70 ℃, reaction 7h.After reaction finishes, revolve to steam and remove toluene, use petroleum ether precipitation, suction filtration is put into vacuum drying oven with product, and drying namely got multipolymer in 8 hours.
The pre-treatment of glass fibre: measure the 100mL1% aqueous ethanolic solution, measure 1mLKH550, in beaker, mix, leave standstill 12 minutes after, add the 24g glass fibre, soak 1h after, take out glass fibre, in stink cupboard, dry 80 ℃ of dry for standby
The surface modification of glass fibre: get multipolymer, add tetrahydrofuran (THF), being formulated as weight ratio is 2% tetrahydrofuran solution, add pretreated glass fibre, add pretreated glass fibre, soak 1.5h, take out glass fibre, dry in stink cupboard, place 80 ℃ of dry 3h of vacuum drying oven, the gained glass fibre can be well compound with polyethylene.
Embodiment 3
The preparation of multipolymer: take by weighing 38.1g methacrylic dodecyl gallate, 10.4g vinylbenzene, 4.9g maleic anhydride respectively, the 0.534g benzoyl peroxide is measured 45mL benzene, adds in the three-necked flask, fully stirs, and logical nitrogen is warming up to 80 ℃, reaction 8h.After reaction finishes, revolve to steam and remove benzene, use petroleum ether precipitation, suction filtration is put into vacuum drying oven with product, and drying namely got multipolymer in 8 hours.
The pre-treatment of glass fibre: measure the 70mL1% aqueous ethanolic solution, measure 1mLKH550, in beaker, mix, leave standstill 10 minutes after, add the 10g short glass fiber, soak 2h after, take out glass fibre, in stink cupboard, dry 85 ℃ of dry for standby.
The surface modification of glass fibre: get multipolymer, add tetrahydrofuran (THF), being formulated as weight ratio is 3% tetrahydrofuran solution, add pretreated glass fibre, soak 2h, take out glass fibre, in stink cupboard, dry, place 90 ℃ of dry 3h of vacuum drying oven, the gained glass fibre can be well compound with polypropylene.
Embodiment 4
The preparation of multipolymer: take by weighing 38.1g methacrylic dodecyl gallate, 10.4g vinylbenzene, 9.8g maleic anhydride respectively, the 0.8745g Diisopropyl azodicarboxylate is measured 50mL benzene, adds in the three-necked flask, fully stirs, and logical nitrogen is warming up to 85 ℃, reaction 9h.After reaction finishes, revolve to steam and remove benzene, use petroleum ether precipitation, suction filtration is put into vacuum drying oven with product, and drying namely got multipolymer in 8 hours.
The pre-treatment of glass fibre: measure the 50mL1% aqueous ethanolic solution, measure 2.5mLKH550, in beaker, mix, leave standstill 15 minutes after, add the 12g short glass fiber, soak 1.5h after, take out glass fibre, in stink cupboard, dry 90 ℃ of dry for standby.
The surface modification of glass fibre: get multipolymer, add tetrahydrofuran (THF), being formulated as weight ratio is 5% tetrahydrofuran solution, add pretreated glass fibre, soak 1.5h, take out glass fibre, in stink cupboard, dry, place 90 ℃ of dry 3h of vacuum drying oven, the gained glass fibre can be well compound with polypropylene.
Claims (6)
1. surface modification glass fibre, it is characterized in that: the surface modification glass fibre is the film that covers one deck coupling agent KH550 on the glass fibre earlier, and then applying one deck copolymer film, the monomer of the multipolymer of coating is methacrylic dodecyl gallate, vinylbenzene and maleic anhydride.
2. surface modification glass fibre as claimed in claim 1, it is characterized in that: the mol ratio of described polymer monomers is the methacrylic dodecyl gallate: vinylbenzene: maleic anhydride: 1:1:1～3:2:2.
3. surface modification glass fibre as claimed in claim 1, it is characterized in that: described coupling agent KH550 film is for to be dissolved in KH550 in 1% aqueous ethanolic solution, the volume ratio of 1% aqueous ethanolic solution KH550 consumption is 50:1-100:1, to dry after the glass fibre immersion, become to cover on the glass fibre one deck coupling agent KH550 film.
4. surface modification glass fibre as claimed in claim 1, it is characterized in that: the weight of glass fibre is the 10-25% of coupling agent KH550 total solution weight in the described surface modification glass fibre.
5. the described surface modification glass fibre of claim 1 preparation method is as follows:
1) preparation of multipolymer: be raw material with methacrylic dodecyl gallate, vinylbenzene, maleic anhydride, the mol ratio of methacrylic dodecyl gallate, vinylbenzene, maleic anhydride is: 1:1:1～3:2:2, stir, and adding initiator, initiator is benzoyl peroxide or Diisopropyl azodicarboxylate, and the add-on of initiator is raw material gross weight 0.6～1.5%; Solvent is toluene or benzene, nitrogen protection, and temperature of reaction is 60～85 ℃, the reaction times is 6～10 hours, desolventizes and drying, obtains the surface-modifying agent multipolymer;
2) pre-treatment of glass fibre: get 1% aqueous ethanolic solution and KH550, KH550 is γ-An Bingjisanyiyangjiguiwan, preparation coupling agent KH550 solution, wherein the volume ratio of 1% aqueous ethanolic solution and KH550 consumption is 50:1-100:1, mix, leave standstill 10-20 minute after, add glass fibre, the glass fibre add-on is the 10-25% of 1% aqueous ethanolic solution and KH550 gross weight, after soaking 0.2-2h, take out glass fibre, oven dry, standby, obtain the pre-treatment glass fibre;
3) surface modification of glass fibre: the fiberglass surfacing properties-correcting agent multipolymer of getting preparation in the step 1, add tetrahydrofuran (THF), be formulated as weight ratio and be 1～5% tetrahydrofuran solution, the pre-treatment glass fibre that adds preparation in the step 2, soak 1～3h, take out glass fibre, dry, obtain the surface modification glass fibre.
6. the described surface modification glass fibre of claim 1 strengthens the application of composite polyolefine material in preparation.
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| CN104370474A (en) * | 2014-10-16 | 2015-02-25 | 宿迁市天彩玻璃纤维有限公司 | Glass fiber surface plasma treatment device |
| CN107503238A (en) * | 2017-09-29 | 2017-12-22 | 成都新柯力化工科技有限公司 | A kind of antimicrobial filter paper and preparation method thereof |
| CN109320102A (en) * | 2018-09-17 | 2019-02-12 | 常州市群丰玻纤制品有限公司 | A kind of high-strength abrasion-proof modified glass-fiber and preparation method thereof |
| CN109320843A (en) * | 2018-10-11 | 2019-02-12 | 安庆市泽烨新材料技术推广服务有限公司 | Polypropylene flame redardant thermal insulation material and preparation method thereof |
| CN109351753A (en) * | 2018-10-27 | 2019-02-19 | 河南教育学院 | The recovery method of glass fibre in a kind of discarded circuit board |
| CN109354774A (en) * | 2018-10-11 | 2019-02-19 | 安庆市泽烨新材料技术推广服务有限公司 | Polypropylene toughening heat-preserving complex material and preparation method thereof |
| CN109467798A (en) * | 2018-10-11 | 2019-03-15 | 安庆市泽烨新材料技术推广服务有限公司 | Polypropylene thermal insulation material and preparation method thereof |
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| CN109867924A (en) * | 2018-12-29 | 2019-06-11 | 江苏和伟美科技发展有限公司 | A kind of fire-retardant enhancing PA6/PBT material of high CTI high-impact and preparation method thereof |
| CN110951138A (en) * | 2019-11-29 | 2020-04-03 | 安徽霖园外新材料有限公司 | Wood-plastic composite material for indoor ceiling |
| CN111592238A (en) * | 2020-05-07 | 2020-08-28 | 北京宇航系统工程研究所 | Coating material for improving softening point and high-temperature radiance of glass fiber and preparation method and application thereof |
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| CN112442896A (en) * | 2019-08-30 | 2021-03-05 | 江汉大学 | Glass fiber cotton containing aryl and application thereof |
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| CN113381112A (en) * | 2021-06-09 | 2021-09-10 | 佛山日克耐热材料有限公司 | Heat-insulating and flame-retardant new energy battery box |
| CN115160757A (en) * | 2022-07-01 | 2022-10-11 | 中国石油化工股份有限公司 | Flame-retardant glass fiber reinforced PC material and preparation method thereof |
| CN115464951A (en) * | 2022-08-22 | 2022-12-13 | 江苏长海复合材料股份有限公司 | Oil-water separation felt and preparation method thereof |
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| CN104370474A (en) * | 2014-10-16 | 2015-02-25 | 宿迁市天彩玻璃纤维有限公司 | Glass fiber surface plasma treatment device |
| CN107503238A (en) * | 2017-09-29 | 2017-12-22 | 成都新柯力化工科技有限公司 | A kind of antimicrobial filter paper and preparation method thereof |
| CN109320102A (en) * | 2018-09-17 | 2019-02-12 | 常州市群丰玻纤制品有限公司 | A kind of high-strength abrasion-proof modified glass-fiber and preparation method thereof |
| CN109320843A (en) * | 2018-10-11 | 2019-02-12 | 安庆市泽烨新材料技术推广服务有限公司 | Polypropylene flame redardant thermal insulation material and preparation method thereof |
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| CN109351753A (en) * | 2018-10-27 | 2019-02-19 | 河南教育学院 | The recovery method of glass fibre in a kind of discarded circuit board |
| CN109608583A (en) * | 2018-12-14 | 2019-04-12 | 戚春凤 | A kind of deep-sea cable armoring material and preparation method thereof |
| CN109867924A (en) * | 2018-12-29 | 2019-06-11 | 江苏和伟美科技发展有限公司 | A kind of fire-retardant enhancing PA6/PBT material of high CTI high-impact and preparation method thereof |
| CN112442896A (en) * | 2019-08-30 | 2021-03-05 | 江汉大学 | Glass fiber cotton containing aryl and application thereof |
| CN110951138A (en) * | 2019-11-29 | 2020-04-03 | 安徽霖园外新材料有限公司 | Wood-plastic composite material for indoor ceiling |
| CN111592238A (en) * | 2020-05-07 | 2020-08-28 | 北京宇航系统工程研究所 | Coating material for improving softening point and high-temperature radiance of glass fiber and preparation method and application thereof |
| CN111635589A (en) * | 2020-07-15 | 2020-09-08 | 苏州润佳工程塑料股份有限公司 | Preparation method of high-modulus high-impact-resistance polypropylene composite material |
| CN113292846A (en) * | 2021-06-03 | 2021-08-24 | 陈红 | Corrosion-resistant composite glass fiber material and preparation method thereof |
| CN113381112A (en) * | 2021-06-09 | 2021-09-10 | 佛山日克耐热材料有限公司 | Heat-insulating and flame-retardant new energy battery box |
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| CN116162318A (en) * | 2023-03-29 | 2023-05-26 | 东南大学 | Polyvinyl alcohol/modified glass fiber composite material and preparation method thereof |
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