CN1308364C - Plant fibre reinforced foam composite material with hard polyurethane structure and production thereof - Google Patents
Plant fibre reinforced foam composite material with hard polyurethane structure and production thereof Download PDFInfo
- Publication number
- CN1308364C CN1308364C CNB2005100190789A CN200510019078A CN1308364C CN 1308364 C CN1308364 C CN 1308364C CN B2005100190789 A CNB2005100190789 A CN B2005100190789A CN 200510019078 A CN200510019078 A CN 200510019078A CN 1308364 C CN1308364 C CN 1308364C
- Authority
- CN
- China
- Prior art keywords
- composite material
- parts
- hard polyurethane
- foam composite
- polyurethane structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a plant fiber reinforced hard polyurethane structural foam composite material and a preparation technology thereof. The composite material comprises component of the following parts by weight: 100 parts of organic polylol resin, 105 to 160 parts of organic polyisocyanate, 0.4 to 0.8 part of catalyst, 0.1 to 0.2 part of accelerating agent, 1 to 3 parts of foam stabilizing agent, 5 to 15 parts of foaming agent and 1 to 5 parts of plant fiber. The composite material comprises the preparation steps of surface treatment for raw hemp and other plant fibers and compression moulding by a one-step method, wherein the surface treatment for plant fibers comprises the processes of alkali treatment, acid washing, etc.; the compression moulding technology by a one-step method comprises raw material preparation, chopped fiber addition, pouring compression moulding and demoulding. The composite material of the present invention has the advantages of excellent property of products, simple provided preparation technology and moulding at room temperature, and adopted jute and other natural plant fibers have the advantages of low price, easy obtainment and biological degradation. Therefore, the composite material has the characteristic of environmental protection at the same time of obviously reducing product cost and also has a wide application range.
Description
Technical field
The present invention relates to the material field, particularly a kind of plant fibre reinforced foam composite material with hard polyurethane structure and preparation technology thereof.
Background technology
In recent years, the high-performance vegetable fibre since have light weight, inexpensive, be easy to get, characteristics such as biodegradable, environmentally safe, and the degree of crystallinity of fiber, orientation degree and longitudinal modulus of elasticity are higher, be well suited for doing the wild phase of polymer matrix composites, thus its composite study with develop paid more and more attention.Abroad the research and development of flaxen fiber matrix material and goods thereof is carried out early.From the sixties, just jute and fabric thereof are used for strengthening thermoplasticity and thermosetting resin abroad.India is taking its place in the front ranks of the world aspect the research of jute fibre matrix material as the country of origin of jute and the main place of production always, and its overwhelming majority work is with jute and rubber combined, perhaps with jute as weighting material.China carries out the research and development of high-performance natural vegetable fibre from the initial stage nineties.Up to the present, abroad some country has entered the industrialization stage, and China generally speaking also is in conceptual phase, and goods also do not have widespread use.
Jute is the robust fibre crop, belongs to a kind of of phloem fiber (fasciated fiber), and that its fiber has is thick and stiff, intensity is high, water absorbability is strong, aproll is fast, advantage such as corrosion-resistant, wear-resisting.The present invention adopts the vegetable fibres such as jute of modification to strengthen urethane foam, improved the every performance of foamy significantly, mechanical property particularly, complete processing is also simpler, therefore uses as the low density structures material to have vast market prospect and important potential industrial application value.
Summary of the invention
Technical problem to be solved by this invention is: a kind of plant fibre reinforced foam composite material with hard polyurethane structure and preparation technology thereof are provided.Strongthener is to select that a kind of cost is low, the tool environment-friendly function for use, and can participate in the natural plant fibre (as jute etc.) of the chemical reaction in the polyurethane foam molding process, relatively strengthens before the structural reform simultaneously and the product properties after the modification, to instruct practice.This composite material preparation process is simple, is suitable for suitability for industrialized production.
The technical solution adopted for the present invention to solve the technical problems is as follows:
Plant fibre reinforced foam composite material with hard polyurethane structure provided by the invention, be made up of strongtheners such as polyurethane combined material and jute fibre and other auxiliary material, its concrete component and parts by weight are: 100 parts of organic multicomponent alcohol resins, 105～160 parts of organic multiple isocyanates, 0.4～0.8 part of catalyzer, 0.1～0.2 part of promotor, 1～3 part of suds-stabilizing agent, 5～15 parts of whipping agents, 1～5 part of strongthener.Strongthener is a vegetable fibre.
It is that vegetable fibre carries out surface treatment and single stage method compression molding that plant fibre reinforced foam composite material with hard polyurethane structure method provided by the invention, its preparation process comprise strongthener, specific as follows:
(1) vegetable fibre is carried out surface treatment: comprise alkaline purification, pickling and fiber chopping.
Alkaline purification: earlier with the vegetable fibre removal of impurities, then vegetable fibre is dried to constant weight in 80～90 ℃, place the NaOH solution of 65～75g/L to soak again, handled 7～9 hours in 20～30 ℃, wash with tap water after taking off liquid.
Pickling: earlier with the vegetable fibre after the washing of dilute nitric acid solution dipping, in and remaining alkali lye on the fiber, reduce crystallization length simultaneously, with tap water washing back oven dry, make modified plant fibers again.
Fiber chopping: with the modified plant fibers chopping, then it is broken up earlier, be made for the chopped strand of 3～10mm length.
(2) single stage method compression molding: comprise the raw material preparation, add chopped strand, mold pressing, moulding and the demoulding.
Raw material is prepared: take by weighing 100 parts of organic polyhydric alcohols, 0.4～0.8 part of catalyzer, 0.1～0.2 part of promotor, 1～3 part of suds-stabilizing agent by weight earlier, 5～15 parts of whipping agents mix then, stir.
Add chopped strand: with 1～5 part by weight of chopped strand, join in the previous step gained mixture, fiber is flooded full and uniformly through stirring.
Mold pressing: 105～160 parts of organic multiple isocyanates have been joined dipping in the previous step in the raw mix of fiber, stir rapidly to pour in the ready metal die after 10～15 seconds and foam, mould pressing process is 15～30 ℃ of molding temperatures, molding pressure 1～10MPa, clamp time 10～15 minutes.
The moulding and the demoulding: 10～15 minutes after fixing of pressurize are finished, and naturally cool to room temperature forming, then the demoulding.
The present invention compares with adopting other urethane foam that strengthens body, has following major advantage:
One. the present invention adopts the response type strongthener to strengthen hard polyurethane foams, resulting structures foamed composite product properties excellence, at extrudate density less than 0.4g/cm
3The time, its compressive strength can reach 8～10MPa, and Young's modulus can reach 0.4GPa.
They are two years old. and preparation technology provided by the invention is simple, adopts the room temperature compression molding, has saved energy consumption, thereby is suitable for suitability for industrialized production and is beneficial to reducing production costs.
They are three years old. the strongthener that adopts among the present invention---natural plant fibre, as inexpensive being easy to get such as jutes, biodegradable, and can participate in chemical reaction in the polyurethane foam molding process, when significantly reducing product cost, have the environmental friendliness feature, have a extensive future.
Description of drawings
Fig. 1 is that unmodified jute/urethane destroys pattern.
Fig. 2 is that modification jute/urethane destroys pattern.
Embodiment
The present invention relates to the vegetable fibre is raw material, and it is the plant fibre reinforced foam composite material with hard polyurethane structure goods that single stage method is produced a kind of high-strength light structured material.Experiment finds that every performance of these goods meets the requirement of using as structured material fully.
The invention will be further described below in conjunction with embodiment.
One. plant fibre reinforced foam composite material with hard polyurethane structure
Be made up of strongtheners such as polyurethane combined material and jute fibre and other auxiliary material, its concrete component and parts by weight are: 100 parts of organic multicomponent alcohol resins, 105～160 parts of organic multiple isocyanates, 0.4～0.8 part of catalyzer, 0.1～0.2 part of promotor, 1～3 part of suds-stabilizing agent, 5～15 parts of whipping agents, 1～5 part of strongthener.Strongthener is a vegetable fibre.
Above-mentioned organic multicomponent alcohol resin is optional with polyester polyol (hydroxyl value 400～600mgKOH/g), polyether polyol resin (hydroxyl value 400～600mgKOH/g), perhaps their mixture.
Organic multiple isocyanate can be selected diphenylmethanediisocyanate, many phenyl polymethine polyisocyanates for use, and they also claim thick MDI (or PAPI), rough tolylene diisocyanate (thick TDI) and refined toluene vulcabond (TDI); Perhaps their mixture.
Catalyzer can be selected trolamine, N for use, N-dimethylcyclohexylamine, tetramethylethylened, triethylenediamine, dimethylethanolamine, five methyl diethylentriamine, perhaps two kinds, two or more mixture.
Promotor can be selected stannous oleate, stannous octoate, dibutyltin dilaurate for use, perhaps two kinds, two or more mixture.
Suds-stabilizing agent can be selected dimethyl siloxane (also claiming silicone oil) for use.
Whipping agent can be selected fluoro trichloromethane (F-11), methyl chlorofluoride (F-12), dichlorotrifluoroethane (HCFC-123), fluoro trichloromethane (HCFC-141b) for use, perhaps two kinds, two or more mixture.
Vegetable fibre can be selected ramie, jute for use, perhaps their mixture.
Two. the preparation of plant fibre reinforced foam composite material with hard polyurethane structure
Its preparation process comprises carries out surface treatment and single stage method compression molding to raw ramie, specific as follows:
1. vegetable fibre is carried out surface treatment:
The main component of vegetable fibres such as jute fibre is a Mierocrystalline cellulose, and its content in fiber can reach 65.32%.Angle from materials chemistry, the Da Liang Hydroxyalkyl base isoreactivity group that the vegetable fibre face exists can with organic multiple isocyanate generation chemical reaction, form cross-linked structure, thereby improve the whole cross-linking density of foam materials, and then improve the mechanical properties such as ultimate compression strength, modulus of compression of material.Because Mierocrystalline cellulose is a natural high moleculer eompound, each basic ring contains three hydroxyls and (contains side group-CH in the repeating unit of cellulose macromolecule
2-OH), hydroxyl on the side group can and organic multiple isocyanate on activity extremely strong-the N=C=O group reacts.But the extensibility that vegetable fibres such as jute fibre are very low, surface that plant protofibril (unprocessed) is level and smooth and impurity thereof are the interface bondings that influences itself and resin matrix, the principal element that the restriction composite materials property improves.In order to improve the interface bonding of vegetable fibre and resin matrix, improve the tensile strength of fiber simultaneously, improve its tensile property, effectively way is that fiber is carried out surface treatment, its technical process comprises alkaline purification, pickling and fiber chopping.
Alkaline purification: earlier with the vegetable fibre removal of impurities, then vegetable fibre is dried to constant weight in 80～90 ℃, place the NaOH solution of 65～75g/L to soak again, handled 7～9 hours in 20～30 ℃, wash with tap water after taking off liquid.
Pickling: earlier with the vegetable fibre after the washing of dilute nitric acid solution dipping, in and remaining alkali lye on the fiber, reduce crystallization length simultaneously, make vegetable fibre significantly improve elongation at break in strong improving to do.With tap water washing back oven dry, make modified plant fibers again, dilute nitric acid solution concentration is 10g/L.
Fiber chopping: with the modified plant fibers chopping, then it is broken up earlier, be made for the chopped strand of 3～10mm length.
2. single stage method compression molding: comprise that raw material is prepared, adding chopped strand, compression molding and the demoulding.
Raw material is prepared: take by weighing 100 parts of organic polyhydric alcohols, 0.4～0.8 part of catalyzer, 0.1～0.2 part of promotor, 1～3 part of suds-stabilizing agent by weight earlier, 5～15 parts of whipping agents mix then, stir.
Add chopped strand: with 1～5 part by weight of chopped strand, join in the previous step gained mixture, fiber is flooded full and uniformly through stirring.
Mold pressing: 105～160 parts of organic multiple isocyanates have been joined dipping in the previous step in the raw mix of fiber, stir rapidly to pour in the ready metal die after 10～15 seconds and foam, mould pressing process is 15～30 ℃ of molding temperatures, molding pressure 1～10MPa, clamp time 10～15 minutes.
The moulding and the demoulding: 10～15 minutes after fixing of pressurize are finished, and naturally cool to room temperature forming, then the demoulding.
Specific examples:
Specific examples 1: the first step, by following proportioning weighing, add not surface treated jute chopped strand in the raw material mixed solution after raw material is prepared, wherein staple length is respectively 3mm, 5mm, 10mm.
Polyether polyol resin (3 parts of 400～600mgKOH/g) 100 parts of hydroxyl values, 115 parts of many phenyl polymethine polyisocyanates, 0.6 part of trolamine, 0.1 part of dibutyltin dilaurate, 3 parts of dimethyl siloxanes, 5 parts of fluoro trichloromethane (HCFC-141b) and jute fibres (being untreated).
In second step, utilize aforementioned single stage method die press technology for forming to make the enhancing foam composite material with hard polyurethane structure.
Specific examples 2: in specific embodiment 1, add surface treated jute chopped strand in the raw material mixed solution after raw material is prepared, wherein staple length is respectively 3mm, 5mm, 10mm.Other implementing process condition is identical with example 1 with process.
Specific examples 3: the first step, by following proportioning weighing, add surface treated jute chopped strand in the raw material mixed solution after raw material is prepared, wherein staple length is respectively 3mm.
Polyether polyol resin (1 part of 400～600mgKOH/g) 100 parts of hydroxyl values, 115 parts of many phenyl polymethine polyisocyanates, 0.6 part of trolamine, 0.1 part of dibutyltin dilaurate, 3 parts of dimethyl siloxanes, 5 parts of fluoro trichloromethane (HCFC-141b), 10 parts of ceramic hollow microballons and jute fibre (processing)
In second step, utilize aforementioned single stage method die press technology for forming to make the enhancing foam composite material with hard polyurethane structure.
The density and the performance of the foregoing description resulting product are as shown in table 1:
The performance of table 1 fiber reinforcement foam composite material with hard polyurethane structure
| Specific examples 1 | Specific examples 2 | Specific examples 3 | |||||
| Staple length (mm) | 3 | 5 | 10 | 3 | 5 | 10 | 3 |
| Sample density (g/cm 3) | 0.32 | 0.37 | 0.39 | 0.31 | 0.36 | 0.38 | 0.35 |
| Compressive strength (MPa) | 5.4 | 7.6 | 8.0 | 5.8 | 9.0 | 9.8 | 7.8 |
From table 1, be not difficult to find out, compare with not surface treated jute fibre enhancing polyurethane foam composite with the surface treated jute fibre enhancing polyurethane foam composite that same processing step is prepared, its compressive strength is significantly improved.
From Fig. 1 and Fig. 2 then as can be seen, surface treated jute fibre is compared with not surface treated jute fibre, and the interface bond effect of itself and body material is far better.
Claims (9)
1. one kind strengthens foam composite material with hard polyurethane structure, comprise organic polyol resin, organic multiple isocyanate and vegetable fibre, it is characterized in that plant fibre reinforced foam composite material with hard polyurethane structure, comprise following component, wherein vegetable fibre is strongthener and surface treated fiber, and each component and parts by weight are:
100 parts of organic multicomponent alcohol resins
105～160 parts of organic multiple isocyanates
0.4～0.8 part of catalyzer
0.1～0.2 part of promotor
1～3 part of suds-stabilizing agent
5～15 parts of whipping agents
1～5 part of strongthener.
2. enhancing foam composite material with hard polyurethane structure according to claim 1 is characterized in that the organic multicomponent alcohol resin is polyester polyol, polyether polyol resin or the mixture of the two, and the hydroxyl value of the two is 400～600mgKOH/g.
3. enhancing foam composite material with hard polyurethane structure according to claim 1 is characterized in that organic multiple isocyanate is diphenylmethanediisocyanate, many phenyl polymethine polyisocyanates, or their mixture.
4. enhancing foam composite material with hard polyurethane structure according to claim 1, it is characterized in that catalyzer is trolamine, N, N-dimethylcyclohexylamine, tetramethylethylened, triethylenediamine, dimethylethanolamine, five methyl diethylentriamine, or two kinds, two or more mixture.
5. enhancing foam composite material with hard polyurethane structure according to claim 1 is characterized in that promotor is stannous oleate, stannous octoate, dibutyltin dilaurate, or two kinds, two or more mixture.
6. enhancing foam composite material with hard polyurethane structure according to claim 1 is characterized in that suds-stabilizing agent is a dimethyl siloxane; Whipping agent is fluoro trichloromethane, methyl chlorofluoride, dichlorotrifluoroethane, fluoro trichloromethane, or two kinds, two or more mixture.
7. enhancing foam composite material with hard polyurethane structure according to claim 1 is characterized in that vegetable fibre is ramie, jute, or their mixture.
8. preparation method who strengthens foam composite material with hard polyurethane structure, the preparation method who it is characterized in that plant fibre reinforced foam composite material with hard polyurethane structure, it is that vegetable fibre carries out surface treatment and single stage method compression molding that its preparation process comprises strongthener, specific as follows:
(1) vegetable fibre is carried out surface treatment: comprise alkaline purification, pickling and fiber chopping,
Alkaline purification: earlier with the vegetable fibre removal of impurities, then vegetable fibre is dried to constant weight in 80～90 ℃, place the NaOH solution of 65～75g/L to soak again, handled 7～9 hours in 20～30 ℃, take off behind the liquid with the tap water washing,
Pickling: earlier with the vegetable fibre after the washing of dilute nitric acid solution dipping, in and remaining alkali lye on the fiber, reduce crystallization length simultaneously, with tap water washing back oven dry, make modified plant fibers again,
The fiber chopping: with the modified plant fibers chopping, then it is broken up earlier, be made for the chopped strand of 3～10mm length,
(2) single stage method compression molding: comprise the raw material preparation, add chopped strand, mold pressing, moulding and the demoulding,
Raw material is prepared: take by weighing 100 parts of organic polyhydric alcohols, 0.4～0.8 part of catalyzer, 0.1～0.2 part of promotor, 1～3 part of suds-stabilizing agent by weight earlier, 5～15 parts of whipping agents mix then, stir,
Add chopped strand: with 1～5 part by weight of chopped strand, join in the previous step gained mixture, fiber is flooded full and uniformly through stirring,
Mold pressing: 105～160 parts of organic multiple isocyanates have been joined dipping in the previous step in the raw mix of fiber, stir rapidly to pour in the ready metal die after 10～15 seconds and foam, mould pressing process is 15～30 ℃ of molding temperatures, molding pressure 1～10MPa, clamp time 10～15 minutes
The moulding and the demoulding: 10～15 minutes after fixing of pressurize are finished, and naturally cool to room temperature forming, then the demoulding.
9. the preparation method of enhancing foam composite material with hard polyurethane structure according to claim 8, it is characterized in that vegetable fibre participates in the chemical reaction in the polyurethane foam molding process, resulting product be plant fibre reinforced foam composite material with hard polyurethane structure in density less than 400kg/m
3The time, its compressive strength reaches 8～10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100190789A CN1308364C (en) | 2005-07-12 | 2005-07-12 | Plant fibre reinforced foam composite material with hard polyurethane structure and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100190789A CN1308364C (en) | 2005-07-12 | 2005-07-12 | Plant fibre reinforced foam composite material with hard polyurethane structure and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1712424A CN1712424A (en) | 2005-12-28 |
| CN1308364C true CN1308364C (en) | 2007-04-04 |
Family
ID=35718237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100190789A Expired - Fee Related CN1308364C (en) | 2005-07-12 | 2005-07-12 | Plant fibre reinforced foam composite material with hard polyurethane structure and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1308364C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013127368A1 (en) * | 2012-03-02 | 2013-09-06 | 中航复合材料有限责任公司 | Composite material containing plant fibre fabrics and preparation method thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102046711B (en) * | 2008-03-27 | 2013-04-24 | 住友化学株式会社 | Foam molded product and process for producing foam molded product |
| CN102417740B (en) * | 2011-10-08 | 2013-06-05 | 福建师范大学 | Surface modification method for reinforcing interface compatibility of plant fibre/polymer based composite through two steps |
| CN102408535A (en) * | 2011-11-23 | 2012-04-11 | 吴江明峰聚氨酯制品有限公司 | Plant fiber-enhanced rigid polyurethane foam plastic |
| CN103483806A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Grape vine-polyurethane composite foam materiel |
| CN104325588A (en) * | 2014-08-26 | 2015-02-04 | 东华大学 | Method for preparing fiber-enhanced polyurethane foam material from waste ultrahigh molecular weight polyethylene composite material |
| CN105367893A (en) * | 2015-11-11 | 2016-03-02 | 浙江捷宇塑料制品有限公司 | Plant-fiber-reinforced P foam lunch box |
| CN108503280A (en) * | 2018-04-13 | 2018-09-07 | 合肥市晨雷思建筑材料科技有限公司 | A kind of novel azulejo and preparation method thereof |
| CN109337353B (en) * | 2018-07-23 | 2020-12-11 | 汕头市华莎驰家具家饰有限公司 | Surface modified fiber reinforced polyurethane composite material and preparation method thereof |
| CN111171275B (en) * | 2020-01-13 | 2021-07-16 | 华南理工大学 | Sand-water abrasion resistant polyurethane material for pipeline lining and preparation method and application thereof |
| CN113352702B (en) * | 2021-06-29 | 2022-11-29 | 广州海鸥住宅工业股份有限公司 | Waterproof chassis of composite floor, composite floor and construction process of composite floor |
| CN114985431B (en) * | 2022-05-12 | 2023-04-18 | 南华大学 | Modified fiber composite material based on microorganism reinforcement process and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034766A (en) * | 1988-01-19 | 1989-08-16 | 中国科学院广州化学研究所 | Process for ammoniation modifying of ramie fibre |
| US5037690A (en) * | 1987-11-27 | 1991-08-06 | De Groot Automotives, B.V. | Shaped product comprising a thermoset, foamed, plastics sheet material reinforced with coherent natural-fibre material, and a process for making the shaped product |
| CN1324893A (en) * | 2000-05-19 | 2001-12-05 | 赵根普 | Foamed polyurethane material containing natural fiber and its making process |
-
2005
- 2005-07-12 CN CNB2005100190789A patent/CN1308364C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5037690A (en) * | 1987-11-27 | 1991-08-06 | De Groot Automotives, B.V. | Shaped product comprising a thermoset, foamed, plastics sheet material reinforced with coherent natural-fibre material, and a process for making the shaped product |
| CN1034766A (en) * | 1988-01-19 | 1989-08-16 | 中国科学院广州化学研究所 | Process for ammoniation modifying of ramie fibre |
| CN1324893A (en) * | 2000-05-19 | 2001-12-05 | 赵根普 | Foamed polyurethane material containing natural fiber and its making process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013127368A1 (en) * | 2012-03-02 | 2013-09-06 | 中航复合材料有限责任公司 | Composite material containing plant fibre fabrics and preparation method thereof |
| US10711394B2 (en) | 2012-03-02 | 2020-07-14 | Avic Composite Corporation Ltd. | Composite having plant fiber textile and fabricating method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1712424A (en) | 2005-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1308364C (en) | Plant fibre reinforced foam composite material with hard polyurethane structure and production thereof | |
| CN100564023C (en) | A kind of kenaf-plastics composite sheet material and preparation method thereof | |
| CN102417740B (en) | Surface modification method for reinforcing interface compatibility of plant fibre/polymer based composite through two steps | |
| CN1239555C (en) | Use of polyisocyanate compsns as binder for composite lignocellulosic materials | |
| CN106832189A (en) | A kind of preparation method of Graphene compound polyurethane material | |
| CN1239556C (en) | Use of polyisocyanate compsns as binder for composite lignocellulosic materials | |
| CN100408610C (en) | Horniness polyurethane foam ternary composite material and preparation method thereof | |
| CN101121813A (en) | Full-degradation natural fibre/polylactic acid composite material and preparation method thereof | |
| CN102558828A (en) | Method for preparing polyurethane hybridization material for hydroxyl-containing filler | |
| CN109251494B (en) | Natural gutta-percha/cellulose modified polylactic acid composite material and preparation method thereof | |
| CN105348473A (en) | Cellulose-reinforced polyurethane/epoxy resin interpenetrating polymer network hard composite foam material and preparation method thereof | |
| CN111410828B (en) | Preparation method of plant wood powder/montmorillonite filled high-performance fully biodegradable polylactic acid composite material | |
| CN110437551B (en) | Self-repairing environment-friendly rubber material and preparation method thereof | |
| CN114395160B (en) | Graphene modified polyurethane composite material and preparation method thereof | |
| CN110964173A (en) | Polyurethane composition for honeycomb composite material, preparation method of polyurethane composition, polyurethane foam and application of polyurethane foam | |
| Chang | Improving the mechanical performance of wood fiber reinforced bio-based polyurethane foam | |
| CN1944009A (en) | Method for modifying wood using foamed isocyanate resin | |
| CN111607062B (en) | Biomass polyurethane foam material and preparation method thereof | |
| CN113717213A (en) | Bonding auxiliary agent for foamed plastic, preparation method and application | |
| KR20070113693A (en) | Preparation method of poly lactic acid-natural fiber composites | |
| CN114196165B (en) | Preparation method of modified jute fiber reinforced bio-based epoxy resin composite material | |
| CN104910347A (en) | Preparation method and application of hyperbranched biphenyls liquid crystal grafting sisal hemp microcrystal | |
| CN100372890C (en) | Unsaturated polyester/polyurethane/organic montmorillonite composite material and production thereof | |
| CN114656679A (en) | Waste paper pulp/nano cellulose full-biomass foam buffer material and preparation method thereof | |
| CN111253637B (en) | Preparation method of wear-resistant rice hulling rubber roll |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070404 Termination date: 20110712 |