CN104140654B - A kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber - Google Patents
A kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber Download PDFInfo
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Abstract
The invention discloses a kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber, comprise the following steps: the preparation of (1) AKD emulsion and the surface treatment to biomass fiber raw material thereof; (2) maturation process of surface modified fibre; (3) surface modification biomass fiber and aliphatic polyester matrix is compound. Through between the fiber of surface hydrophobicity processing, Hydrogenbond effect weakens, and the reunion in aliphatic polyester matrix reduces, and has improved the boundary strength of composite, thereby has made it have more excellent combination property, especially mechanical property. This composite products is widely used, and can be used for the fields such as household electrical appliance, auto industry, packaging, commodity. And the method cost is lower, simple process, is conducive to apply, for the level of utilizing that improves biomass material, alleviate the aspects such as petroleum resources crisis and protection of the environment significant.
Description
Technical field
The invention belongs to advanced composite material field, relate to cellulose modified and polymer composite, be specifically related to, by the interpolation of alkyl ketene dimer (AKD), improve the method for biomass fiber-aliphatic polyester composite material performance.
Background technology
Macromolecular material has become the mainstay of modern science and technology and the development of the national economy, and its raw material major part derives from oil, and major part is wherein difficult to degraded. The day by day pressure deficient and environmental protection of petroleum resources impels development low-carbon (LC), eco-friendly macromolecular material to become important work.
Biomass fiber-polymer composites is the novel Green Composites of a class, and general-purpose plastics (as PE, PP, PVC etc.) or biodegradable plastics (mainly referring to aliphatic poly ester material) all can be used as the matrix material of biomass fiber-polymer composites. With common fortifying fibre as compared with glass fibre, carbon fiber etc., biomass fiber has advantages of that specific strength is high, wide material sources, cheap, biodegradable, process equipment is worn and torn little, there is biodegradable with the composite obtaining after aliphatic polyester Material cladding, can greatly reduce the production cost of composite simultaneously.
Aliphatic polyester (as PLA, PBS, PBAT etc.) is commercial macromolecular material, can natural decomposition under composting conditions, both there are plastics, free from environmental pollution again, be deemed to be a 21 century application class " function polymeric material " extremely widely. The shortcomings such as but aliphatic polyester ubiquity price is higher, and mechanical property is poor, have affected its industrial application.
The mechanical property important of composition, character, combination and the bond strength of fiber-reinforced thermoplastic resin based composite material interface to composite. The ability of the stress transmission between Fiber In Composite Material and matrix depends primarily on the performance at interface. The quality of Overall Properties of Composites depends on the interface bonding state between matrix and filler to a great extent, and interface is exactly often the most weak link of material.
The main component of wood pad is cellulose, hemicellulose, the macromolecular compound that lignin etc. contain great amount of hydroxy group, phenolic hydroxyl group, a large amount of monose, pectic substance, fat, wax and micromolecular compound. The existence of hydroxyl, phenolic hydroxyl group, makes wood pad have strong polarity and hydrophily, and higher surface energy. And polymeric matrix is the macromolecular material of nonpolar or low pole mostly, surface can be lower. Interface between the two can not be bonding well, and external force can not effectively be transmitted between two-phase, causes the poor-performing of material. In addition, the existence of hydroxyl and phenolic hydroxyl group, has increased the agglomeration between wood fiber raw material, when hot-working, can produce clustering phenomena, causes it can not be dispersed in plastic substrate, thereby has influence on the combination property of composite. Therefore, the development of wood plastic composite is subject to the restriction of compatibility. Improving the dispersiveness of lignocellulose raw material in matrix, improve the two-phase interface combination of wood plastic composite simultaneously, is the key issue that improves wood plastic composite serviceability, is also emphasis and difficult point in research.
In to the further investigation of composite, people have proposed multiple interface theory, as theory of chemical bonds, wellability theory, transition zone theory, mechanical interlocked theory, frictional theory, diffusion theory, static theory etc. Based on above-mentioned various interface theories, produce the method for varied composite material interface modification. Roughly can be divided into physical modification and chemical modification two classes.
Process fiber or matrix surface by physical means, can change fibre structure pattern, engage with polymeric matrix on fortifying fibre element surface, and its effect directly affects modified effect below and the performance of composite. The feature of physical modification is not need to add any other reagent, and cost is relatively low, substantially can not impact environment, but result of use is not obvious separately, is more to prepare for chemical modification below.
Chemical modification is, by adding chemical reagent, wood powder is carried out to surface treatment, to change the chemical constitution on string surface, improve compatibility and the dispersiveness of string in resin matrix of string and resin matrix, thereby improve the mechanical property of composite. Can be divided into alkali treatment, acidylate processing, interface modifier processing etc. according to the means of its realization. In various chemical treatment methods, adding interface modifier is simple and efficient way, is also to report maximum methods in current wood plastic composite Study on Compatibility field. It is crosslinked that interface modifier is mainly set up physics and chemistry by chemical reaction or immersional wetting between string/polymer, between fiberfill and polymer, play the effect of a bridge, thereby improve both compatibilities, promote the dispersion of fiberfill in matrix. The interface modifier that is generally used for improving lignocellulose raw material and polymeric matrix has copolymer, the graft etc. of silane coupler, titanate esters and aluminate coupling agent, isocyanates coupling agent and various polarity and non-polar monomer.
Li Qin etc. disclose a kind of bamboo powder filling biodegradable compound material and preparation method thereof in Chinese patent application CN101942184A, adopt aluminate coupling agent to improve the interface compatibility of bamboo powder fiber and PBS matrix, obtain rigid balancing, the good composite of mechanical property. Yu Hancheng etc. disclose a kind of completely biodegradable material and preparation method thereof in Chinese patent application CN101519524B, adopt silane coupler KH560 to prepare starch/PBS composite, after modification, the comprehensive mechanical property of composite obtains larger raising.
In the paper that YangZhao etc. deliver at " JournalofAppliedPolymerScience " 154 volume fourth phase 3211-3220 pages in 2012, adopt four kinds of different amino silicane coupling agents to carry out modification to rice straw fiber, and prepared stalk fibre/PBS composite. After modification, the tensile property of composite improves, and the hot strength of the composite obtaining through 3-(2-aminoethyl aminopropyl) triethoxysilane modification is the highest, this is because the amino content in coupling agent is maximum, carbonyl reaction in amino and PBS forms the hydrogen bond of blue shift, the interface binding intensity of composite is increased, thereby improved significantly the performance of composite.
The composite of preparing than general-purpose plastics, at present about the report of aliphatic poly ester group composite is still less, the research and development of still needing improve the new method of its interface combination, improve composite material interface adhesion strength, the final serviceability that improves composite, promotes the promotion and application of this environment-friendly material.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing aliphatic polyester based composites with alkyl ketene dimer surface modification biomass fiber, with industrial goods alkyl ketene dimer (AKD) wax powder, the AKD emulsion of configuration suitable concentration, or directly adopt the AKD emulsion of industrial goods, biomass fiber is carried out to surface preparation, make it in fiber surface slaking, through the fiber of surface hydrophobicity processing, improving it to aliphatic polyester matrix wellability and close-burning while, improve the boundary strength of composite, thereby make it have more excellent combination property, especially mechanical property.
To achieve these goals, technical scheme of the present invention is:
A method of preparing aliphatic polyester based composites with alkyl ketene dimer surface modification biomass fiber, comprises the following steps:
Step 1, the surface treatment of AKD emulsion to biomass fiber:
AKD emulsion is carried out surface treatment to biomass fiber and is obtained surface modification biomass fiber, and wherein the mass ratio of AKD emulsion and biomass fiber is (0.05-20): 100;
Step 2, the dry maturation process of surface modification biomass fiber:
By surface modification biomass fiber after treatment forced air drying 4 ~ 24h at 80 ~ 140 DEG C in step 2, obtain the modified biomass fiber after surface treatment;
Step 3, surface modification biomass fiber and aliphatic polyester matrix compound:
Mix with aliphatic polyester matrix melt-processed at 80 ~ 200 DEG C with the surface modification biomass fiber after drying slaking in step 3, prepare composite, wherein the mass ratio of surface modification biomass fiber and aliphatic polyester matrix is (1-200): 100;
Described AKD is alkyl ketene dimer.
In one embodiment of the invention, in described step 1, AKD emulsion is carried out surface treatment method to biomass fiber: mixed liquor rotating speed with 10 ~ 5000rpm in homogenizer stirs 5 ~ 60min, obtains surface modification biomass fiber.
In one embodiment of the invention, the AKD in described step 1 is emulsion.
In one embodiment of the invention, the AKD in described step 1 is wax powder, prepared by wax powder to the method for AKD emulsion:
First, by cationic starch, dispersant and appropriate water fully mix under stirring condition, at 70 DEG C ~ 90 DEG C heating 1 ~ 120min, are placed in incubator after forming emulsifying agent;
Secondly, by AKD wax powder heat fused, and emulsifying agent is fully mixed with AKD wax powder, be prepared into mass fraction and be 0.1% ~ 10% AKD emulsion.
In one embodiment of the invention, described dispersant is sodium lignin sulfonate or alcamines aqueous dispersion.
In one embodiment of the invention, it is the one in four carbon to two ten carbon that described AKD props up chain length, or multiple mixture.
In one embodiment of the invention, to prop up chain length be the one in 12 carbon to ten six carbon to preferred AKD.
In one embodiment of the invention, the biomass fiber in described step 1 is selected from one or more in wood powder, powdered rice hulls, stalk fibre and bamboo powder.
In one embodiment of the invention, the melt-processed molding mode in described step 3 is selected banburying, is opened the one in refining or extrusion molding.
By technique scheme, the invention has the beneficial effects as follows:
The present invention can make to form good boundary layer between biomass fiber and aliphatic polyester matrix, thereby can better bring into play the humidification of biomass fiber to aliphatic polyester matrix, improves combination property, the especially mechanical property of composite;
Do not affect the biodegradability of aliphatic polyester matrix, and with low cost simultaneously, be conducive in batches, continuously, the industrial production of scale.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 a is the contrast that in embodiment 1, AKD processes front and back PBS-wood flour composite material hot strength;
Fig. 1 b is the contrast that in embodiment 1, AKD processes front and back PBS-wood flour composite material impact strength;
Fig. 2 a is the contrast that in embodiment 4, AKD processes front and back PLA-powdered rice hulls composite hot strength;
Fig. 2 b is the contrast that in embodiment 4, AKD processes front and back PLA-powdered rice hulls composite impact strength.
Detailed description of the invention
For technological means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, further set forth the present invention. For not dated especially technological parameter, can carry out with reference to routine techniques.
Realize technological means of the present invention and should be not limited to following examples, and can within the scope of the technical conditions of foregoing invention content, adjust.
Because alkyl ketene dimer (AKD) has hydrophobic grouping and reaction active groups simultaneously, for the treatment of biomass fiber surface, the hydroxyl generation esterification of reaction active groups and fiber, form covalent bonds, form the stable film of one deck at fiber surface, now hydrophobic group (chain alkyl) turns to outside fiber surface, makes biomass fiber surface become more hydrophobic, thereby improved the wellability of polymeric matrix to fiber surface, interface bond strength is improved.
Particularly, a kind of method of preparing aliphatic polyester based composites with alkyl ketene dimer surface modification biomass fiber, comprises the following steps:
Step 1, the surface treatment of AKD emulsion to biomass fiber:
AKD emulsion is carried out surface treatment to biomass fiber and is obtained surface modification biomass fiber, and wherein the mass ratio of AKD emulsion and biomass fiber is (0.05-20): 100;
Wherein in step 1, AKD emulsion is carried out surface treatment method to biomass fiber: mixed liquor rotating speed with 10 ~ 5000rpm in homogenizer stirs 5 ~ 60min, obtains surface modification biomass fiber.
Further, biomass fiber is wherein selected from one or more in wood powder, powdered rice hulls, stalk fibre and bamboo powder, or separates by chemical method or Mechanical Method the fiber obtaining.
Step 2, the dry maturation process of surface modification biomass fiber:
By surface modification biomass fiber after treatment forced air drying 4 ~ 24h at 80 ~ 140 DEG C in step 2, obtain the modified biomass fiber after surface treatment;
AKD emulsion can play the effect of applying glue in paper industry, need to after dry, continue slaking a period of time, but paper dry run on paper machine after applying glue is shorter, the approximately curing time of several days in later stage, hydrophobically modified better effects if.
Step 3, surface modification biomass fiber and aliphatic polyester matrix compound:
Mix with aliphatic polyester matrix melt-processed at 80 ~ 200 DEG C with the surface modification biomass fiber after drying slaking in step 3, prepare composite, wherein the mass ratio of surface modification biomass fiber and aliphatic polyester matrix is (1-200): 100; Described AKD is alkyl ketene dimer.
Further, the melt-processed molding mode in step 3 is selected banburying, is opened the one in refining or extrusion molding.
Wherein the AKD in step 1 is emulsion; If the AKD in step 1 is wax powder, prepared by wax powder to the method for emulsion:
First, by cationic starch, dispersant and appropriate water fully mix under stirring condition, at 70 DEG C ~ 90 DEG C heating 1 ~ 120min, are placed in incubator after forming emulsifying agent; Wherein dispersant is sodium lignin sulfonate or alcamines aqueous dispersion;
Secondly, by AKD wax powder heat fused, and emulsifying agent is fully mixed with AKD wax powder, be prepared into mass fraction and be 0.1% ~ 10% AKD emulsion.
In conjunction with implementation content of the present invention, provide following 5 embodiment.
The Chinese translation of following each aliphatic polyester matrix is as follows:
PBS: poly butylene succinate
PLA: PLA
CTMP fiber: CTMP fiber
Embodiment 1：
(1) preparation of AKD emulsion and the surface treatment to Poplar Powder thereof:
With commodity series A KD emulsion (Shandong company product, solid content 15%, AKD content 12%) 80-100 order Poplar Powder is carried out to surface treatment, AKD is 2%(mass fraction with respect to the consumption of Poplar Powder), in homogenizer, under 2000r/min condition, stir 15min.
(2) the dry maturation process of Poplar Powder modified fibre:
According to the Poplar Powder modified fibre forced air drying 4h at 105 DEG C after above-mentioned surface modification, seal for subsequent use.
(3) Poplar Powder modified fibre and PBS's is compound:
Press following mass percent proportioning material: Poplar Powder modified fibre 30% after dry processing, PBS70% processes 10min in banbury under 120 DEG C of conditions, hot-forming, prepares PBS/ Poplar Powder composite.
By Fig. 1 a, Fig. 1 b contrast is known, and compared with the composite of preparing without the Poplar Powder of AKD processing, the composite hot strength of preparing with the Poplar Powder of processing through AKD improves 20.7%, and impact strength improves 13.3%.
Embodiment 2：
(1) preparation of AKD emulsion and the surface treatment to bamboo powder thereof:
With commodity series A KD emulsion (Shandong company product, solid content 15%, AKD content 12%) 60-80 order bamboo powder is carried out to surface treatment, AKD is 2%(mass fraction with respect to the consumption of bamboo powder), in homogenizer, under 2000r/min condition, stir 15min.
(2) the dry maturation process of bamboo powder modified fibre:
Forced air drying 24h at 90 DEG C of the bamboo powder modified fibres that obtain, seals for subsequent use.
(3) bamboo powder modified fibre and PLA's is compound:
Press following mass percent proportioning material: bamboo powder modified fibre 35% after dry maturation process, PLA65%, under 200 DEG C of conditions, mill processing 8min, hot-forming, prepares PLA/ bamboo powder composite material.
Compare the composite that does not add AKD, the composite hot strength of preparing with AKD surface-treated bamboo powder improves 11.6%, and impact strength improves 14.5%, and bending modulus increases.
Embodiment 3:
(1) surface treatment of the preparation of AKD emulsion and bamboo powder thereof:
Take 15 grams of cationic starches, 1.5 grams of lignosulfonates, 17.5 grams, aluminum sulfate, water 846mL fully mixes under stirring condition, at 80 DEG C of heating 60min, after formation emulsifying agent, is placed in incubator. By 120 grams of AKD wax powder (Shandong company product, chain length: C14-C16) heat fused, emulsifying agent is fully mixed with AKD wax powder, be prepared into mass fraction and be 15% emulsion.
By this emulsion, 60-80 order bamboo powder is carried out to surface treatment, under 2000r/min condition, stir 20min with homogenizer.
(2) maturation process of bamboo powder modified fibre:
Obtain forced air drying 24h at 100 DEG C of bamboo powder modified fibres, seal for subsequent use.
(3) bamboo powder modified fibre and PBS's is compound:
Press following mass percent proportioning material: bamboo powder modified fibre 25% after dry maturation process, PBS75%, extrusion molding at 150 DEG C on double screw extruder, prepares PBS/ bamboo powder composite material.
Compared with the composite of preparing with the bamboo powder of processing without AKD, the composite hot strength of preparing with the bamboo powder of processing through AKD improves 17.3%, and impact strength improves 15.4%.
Embodiment 4:
(1) preparation of AKD emulsion and the surface treatment to powdered rice hulls thereof:
With commodity series A KD emulsion (the Jiangsu company product of buying, solid content 15%, AKD content 12%) 80-100 order powdered rice hulls is carried out to surface treatment, AKD is 3%(mass fraction with respect to the consumption of powdered rice hulls), in homogenizer, under 2000r/min condition, stir 20min.
(2) the dry processing of powdered rice hulls modified fibre:
The modification powdered rice hulls fiber forced air drying 6h at 105 DEG C obtaining, seals for subsequent use.
(3) powdered rice hulls modified fibre and PBS's is compound:
Press following mass percent proportioning material: powdered rice hulls modified fibre 30% after dry maturation process, PBS70%, extrusion molding under 120 DEG C of conditions, prepares PBS/ powdered rice hulls composite.
By Fig. 2 a, Fig. 2 b contrast is known, and compared with the composite of preparing without the powdered rice hulls of AKD processing, the composite hot strength of preparing with the powdered rice hulls of processing through AKD improves 12.7%, and impact strength improves 11.6%.
Embodiment 5:
(1) preparation of AKD emulsion and the surface treatment to biomass fiber raw material thereof:
Take 15 grams of cationic starches, 1.5 grams of lignosulfonates, 17.5 grams, aluminum sulfate, water 846mL fully mixes under stirring condition, within 1 hour, forms after emulsifying agent 80 DEG C of heating, is placed in incubator. By 120 grams of AKD wax powder (company of U.S. product, chain length: C16-C18) heat fused, emulsifying agent is fully mixed with AKD wax powder, be prepared into mass fraction and be 15% emulsion.
By this emulsion, dragon spruce CTMP fiber (CTMP fiber) is carried out to surface treatment, AKD is 3%(mass fraction with respect to the consumption of CTMP fiber), under 2000r/min condition, stir 20min with homogenizer.
(2) the dry maturation process of CTMP modified fibre:
The modification CTMP fiber forced air drying 24h at 100 DEG C obtaining, seals for subsequent use.
(3) CTMP modified fibre and PLA's is compound:
Press following mass percent proportioning material: dry CTMP fibre modification fiber 30% after treatment, PLA70% processes 8min in banbury under 190 DEG C of conditions, hot-forming, prepares PLA/CTMP fibrous composite.
Compare not surface treated composite, the composite hot strength of preparing with AKD surface-treated CTMP fiber improves 14.5%, and impact strength improves 16.1%.
More than show and described the general principle of patent of the present invention and the advantage of principal character and patent of the present invention. The technical staff of the industry should understand; patent of the present invention is not restricted to the described embodiments; the principle that patent of the present invention is just described of describing in above-described embodiment and description; do not departing under the prerequisite of patent spirit and scope of the present invention; patent of the present invention also has various changes and modifications, and these changes and improvements all fall in claimed the scope of the claims of the present invention. The claimed scope of patent of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. a method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber, is characterized in that, comprises the following steps:
Step 1, the surface treatment of AKD emulsion to biomass fiber:
AKD emulsion is carried out surface treatment to biomass fiber and is obtained surface modification biomass fiber, and wherein the mass ratio of AKD emulsion and biomass fiber is (0.05-20): 100;
Step 2, the dry maturation process of surface modification biomass fiber:
By surface modification biomass fiber after treatment forced air drying 4 ~ 24h at 80 ~ 140 DEG C in step 1, obtain the modified biomass fiber after surface treatment;
Step 3, surface modification biomass fiber and aliphatic polyester matrix compound:
Mix with aliphatic polyester matrix melt-processed at 80 ~ 200 DEG C with the surface modification biomass fiber after drying slaking in step 2, prepare composite, wherein the mass ratio of surface modification biomass fiber and aliphatic polyester matrix is (1-200): 100;
Described AKD is alkyl ketene dimer;
AKD in described step 1 is wax powder, prepared by wax powder to the method for emulsion:
First, by cationic starch, dispersant and appropriate water fully mix under stirring condition, at 70 DEG C ~ 90 DEG C heating 1 ~ 120min, are placed in incubator after forming emulsifying agent;
Secondly, by AKD wax powder heat fused, and emulsifying agent is fully mixed with AKD wax powder, be prepared into mass fraction and be 0.1% ~ 10% AKD emulsion.
2. a kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber according to claim 1,
The method of preparing aliphatic polyester based composites with alkyl ketene dimer surface modification biomass fiber is characterized in that: in described step 1, AKD emulsion is carried out surface treatment method to biomass fiber: mixed liquor rotating speed with 10 ~ 5000rpm in homogenizer stirs 5 ~ 60min, obtains surface modification biomass fiber.
3. a kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber according to claim 1, is characterized in that: the AKD in described step 1 is emulsion.
4. a kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber according to claim 1, is characterized in that: described dispersant is sodium lignin sulfonate or alcamines aqueous dispersion.
5. a kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber according to claim 1, is characterized in that: it is the one in four carbon to two ten carbon that described AKD props up chain length, or multiple mixture.
6. a kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber according to claim 5, is characterized in that: it is the one in 12 carbon to ten six carbon that preferred AKD props up chain length.
7. a kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber according to claim 1, is characterized in that: the biomass fiber in described step 1 is selected from one or more in wood powder, powdered rice hulls, stalk fibre and bamboo powder.
8. a kind of method of preparing aliphatic polyester composite material with alkyl ketene dimer surface modification biomass fiber according to claim 1, is characterized in that: the melt-processed molding mode in described step 3 is selected banburying, opened the one in refining or extrusion molding.
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| CN105062107A (en) * | 2015-09-17 | 2015-11-18 | 无限极（中国）有限公司 | Fibrous composite and preparation method and application thereof |
| CN109233231B (en) * | 2018-08-17 | 2020-12-18 | 东华大学 | Method for preparing lignin/polylactic acid composite film by using Pickering emulsion |
| CN109575534B (en) * | 2018-12-11 | 2020-12-22 | 湖南绿燊环保科技有限公司 | Biomass reinforcing agent, modified PBS material and preparation method thereof |
| CN111622013A (en) * | 2020-06-04 | 2020-09-04 | 龙游富田造纸精化有限公司 | Modified cationic starch emulsifier and method for preparing AKD emulsion by using same |
| CN114106358B (en) * | 2020-08-26 | 2023-05-26 | 上海昶法新材料有限公司 | Modified bio-based material, composite material, raw materials thereof, preparation method and application |
| CN113214619B (en) * | 2021-05-08 | 2022-12-30 | 上海同化新材料科技有限公司 | Microfibrillated cellulose and polylactic acid composite material and preparation method thereof |
| CN114573958A (en) * | 2022-03-28 | 2022-06-03 | 广东省科学院生物与医学工程研究所 | Elastomer and epoxy micromolecule synergistic toughening-reinforcing modified plant fiber-based biodegradable composite material and preparation method thereof |
| CN114907625B (en) * | 2022-05-24 | 2023-07-14 | 天津科技大学 | Preparation and application of bio-based waterproof and oilproof agent |
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| The Interfacial Modification of Rice Straw Fiber Reinforced Poly(butylene succinate) Composites: Effect of Aminosilane with Different Alkoxy Groups;Yang Zhao etc.;《Journal of Applied Polymer Science》;20120201;第125卷;第3211-3220页 * |
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Effective date of registration: 20210810 Address after: 713400 energy and chemical building materials Industrial Park, Jianjun Town, Yongshou County, Xianyang City, Shaanxi Province Patentee after: SHAANXI HUAHAOXUAN NEW ENERGY TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 710021 Shaanxi province Xi'an Weiyang university campus of Shaanxi University of Science and Technology Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
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