CN1228388C - Composite material and itd preparation method - Google Patents
Composite material and itd preparation method Download PDFInfo
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- CN1228388C CN1228388C CNB031280315A CN03128031A CN1228388C CN 1228388 C CN1228388 C CN 1228388C CN B031280315 A CNB031280315 A CN B031280315A CN 03128031 A CN03128031 A CN 03128031A CN 1228388 C CN1228388 C CN 1228388C
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- soybean
- polyether glycol
- soyflour
- vulcabond
- polyester polyol
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Abstract
The present invention discloses a composite material and a preparation method thereof, wherein the composite material is prepared by using soybean byproducts, such as soybean dregs, soybean flour, etc. and polyether glycol or polyester polyol as raw materials. The method comprises the following steps: firstly, the polyether glycol or the polyester polyol reacts with diisocyanate so as to obtain a polyurethane prepolymer; then, the polyurethane prepolymer is mixed with the soybean dregs or the soybean flour according to a definite proportion and reacts with the soybean dregs or the soybean flour under the condition of lacking solvent and additional plasticizing agents before being thermally pressed into a flaky material or a material in other shapes; otherwise, the polyether glycol or the polyester polyol is mixed with the diisocyanate and the soybean dregs or the soybean flour according to a definite proportion, and after the mixture is directly extruded for reaction and thermally pressed by a screw machine, the composite material can be obtained. The types and the proportion of the soybean byproducts, the polyether glycol or the polyester polyol and the diisocyanate can be changed so as to obtain materials with various performance from plastics to elastomer; thereby, the composite material of the soybean dregs or the soybean flour is a new material with the advantages of simple process and low cost.
Description
Technical field
The present invention relates to a kind of is matrix material of obtaining of raw material and preparation method thereof with soybean byproducts such as soybean residue, soyflour and polyether glycol or polyester polyol, vulcabond, belongs to chemical field, also belongs to the polymer material science field.
Background technology
Along with the exhaustion day by day of petroleum resources, and non-degraded synthetic macromolecule is researched and developed the field, forward position that " green polymer " becomes polymer science to the pollution problem of environment.China abounds with soybean, therefore has abundant soya products resource.But China's soybean oil length (17%) is starkly lower than U.S.'s (23%), and price is higher by 40% than the world market, one of its countermeasure is the utilization ratio that improves after extracting oil and extracted the byproduct after the soybean protein, makes it change Industrial materials into, improves the value of agricultural byproducts thus.Usually, after extracting soybean oil, can obtain a large amount of defatted soyflours, soybean protein isolate and soybean residue etc., they had both had certain commercial value, therefore the characteristic that has biodegradable again is a kind of the meet strategy of sustainable development, eco-friendly, natural macromolecular material of awaiting researching and developing energetically.Such as, the report (Ind.Eng.Chem., 32,1002,1940) of soy protein plastic was once arranged 20th century 30 and the forties.But when at a time when petroleum products fast development period, the processing exploitation of soybean byproduct does not cause enough attention.In recent years, soybean protein research is very noticeable in the world, and it becomes the important source material of emerging " industrial albumen plastics ".Abroad mainly concentrate on soybean prod as caking agent (J.Am.Oil Chem.Soc., 72 (12), 1461,1995), plastics (J.Polymer, 42,2569,2001), textile fibres (J.Appl.Polym.Sci., 71,11,1999) and various wrapping material (Polym.Prepr., 39 (2), 148, research in the field such as 1998), and domestic about the soybean byproduct in the applied research of aspects such as plastics, wrapping material shortcoming (Ind.Eng.Chem.Res., 40 very also, 1879,2001).
Urethane is a kind of excellent property, widely used macromolecular material.In polyurethane system, add preparation polyurethane foams such as soyflour, soybean protein and cause foreign scholar's attention (J.Appl.Polym.Sci., 81,2027,2001; J.Appl.Polym.Sci., 80,10,2001).Soyflour is the material behind the soybean extract oil, and the residue that soybean residue is a soyflour after alkali solution technique extracts soybean protein isolate is that raw material and polyether glycol or polyester polyol, vulcabond do not appear in the newspapers by the work that chemical reaction and hot pressing prepare matrix material with them.
Summary of the invention
Problem to be solved by this invention provides a kind of matrix material and preparation method thereof, this matrix material is a main raw material with soybean byproducts such as soybean residue, soyflour and polyether glycol or polyester polyol, vulcabond, make under solvent-free and no additional plasticizer condition, production technique is simple, with low cost.
Technical scheme provided by the invention is: a kind of matrix material is a raw material with soybean residue or the pure and mild vulcabond of soyflour, polyether glycol or polyester polyols, through screw rod machine extrusion reaction, hot-forming obtaining; Wherein the mol ratio of polyether glycol or the pure and mild vulcabond of polyester polyols is 1: 1.5 to 1: 2, and the quality sum of polyether glycol or the pure and mild vulcabond of polyester polyols and the mass ratio of soybean residue or soyflour are 3: 7 to 5: 5.
Matrix material of the present invention can be by polyether glycol or polyester polyol and the vulcabond mixed in molar ratio by 1: 1.5 to 1: 2, make all or part of with the end capped polyurethane prepolymer of isocyano 70～90 ℃ of reactions, mix by this polyurethane prepolymer and soybean residue or soyflour mass ratio then by 3: 7 to 5: 5, and through screw rod machine extrusion reaction, hot-forming obtaining.
Perhaps directly mix down at 70～90 ℃ by polyether glycol or the pure and mild vulcabond of polyester polyols, soybean residue or soyflour, and through screw rod machine extrusion reaction, hot-forming obtaining.
The present invention also provides the preparation method of above-mentioned matrix material: with polyether glycol or polyester polyol and the vulcabond mixed in molar ratio by 1: 1.5 to 1: 2,70～90 ℃ of following isothermal reactions 2～3 hours, obtain all or part of with the end capped polyurethane prepolymer of isocyano; This polyurethane prepolymer and soybean residue or the soyflour mass ratio by 3: 7 to 5: 5 is mixed, through screw rod machine extrusion reaction, reinstall in the mould 110～140 ℃ hot-forming down, obtain required matrix material.
The easier method for making of above-mentioned matrix material is: under 70～90 ℃, simultaneously polyether glycol or polyester polyol mixed with vulcabond, soybean residue or soyflour, and through screw rod machine extrusion reaction, hot-forming obtaining; Wherein the mol ratio of polyether glycol or the pure and mild vulcabond of polyester polyols is 1: 1.5 to 1: 2, the quality of polyether glycol or the pure and mild vulcabond of polyester polyols and with the mass ratio of soybean residue or soyflour be 3: 7 to 5: 5.
The present invention can be by selecting different soybean byproducts, different polyether glycol or polyester polyol, the various materials of adjusting ratio, change reaction and hot pressing condition obtains having different mechanical properties, the polyurethane material of water resistance and biodegradability, it is high in technological content, has novelty.Production technique of the present invention is simple, with low cost, and the matrix material that obtains can be prepared into the shape of various hot pressing dies as required, has practicality in tourism goods, small stores, horticulture and technology industry.
Technical progress of the present invention is: (1) makes full use of that the source is abundant, low-cost soyflour and soybean residue are main raw material; (2) by with ether-containing key, ester bond and-substance reaction of NCO group, improved the workability of soybean residue and soyflour greatly; (3) can obtain having the material of better mechanical property and water resistance.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1
With exsiccant polypropylene glycol and mol ratio in three-necked flask the mixing of the new 2,4 toluene diisocyanate that steams by 1: 2, stir be heated to 85 ℃ down after insulation steaming 2.5 hours, obtain the end capped polyurethane prepolymer of isocyano.With this polyurethane prepolymer and exsiccant soybean residue by 4: 6 quality than mixing, through screw rod machine extrusion reaction.Extrusion condition is: respectively be 90,100 and 110 ℃ from the sample introduction to the temperature out.Extruded material in 20MPa, 120 ℃ of following hot pressing 7 minutes, is chilled to and takes out the hot pressing resulting sheet below 50 ℃ on thermocompressor.Mechanical property, the water resistance of this material are seen attached list.
Embodiment 2
Whole process of preparation is with embodiment 1, and only the mass ratio with polyurethane prepolymer and soybean residue was changed to 5: 5.
Embodiment 3
Whole process of preparation is changed to soyflour with embodiment 1 with soybean residue, and extrusion condition is changed to: respectively be 80,90 and 100 ℃ from the sample introduction to the temperature out, hot pressing temperature is 110 ℃.
Embodiment 4
Whole process of preparation is with embodiment 3, and only the mass ratio with polyurethane prepolymer and soyflour was changed to 5: 5.
Embodiment 5
With the exsiccant molecular weight is 2 of 400 polycaprolactone, new steaming, 4-tolylene diisocyanate and exsiccant soybean residue are evenly mixed, polycaprolactone and 2 wherein, the mol ratio of 4-tolylene diisocyanate is 1: 1.5, polycaprolactone and 2, the quality sum of 4-tolylene diisocyanate and the mass ratio of soybean residue are 4: 6, and miscellany is through screw rod machine extrusion reaction.Extrusion condition is: respectively be 110,120 and 130 ℃ from the sample introduction to the temperature out.Extruded material in 20MPa, 130 ℃ of following hot pressing 10 minutes, is chilled to and takes out the hot pressing resulting sheet below 50 ℃ on thermocompressor.
Embodiment 6
Whole process of preparation only is changed to the quality sum of polycaprolactone and 2,4 toluene diisocyanate and the mass ratio of soybean residue 5: 5 with embodiment 5.
Embodiment 7
Whole process of preparation is with embodiment 6, only the mol ratio of polycaprolactone and 2,4 toluene diisocyanate is changed to 1: 1.7.
Embodiment 8
With 2 of exsiccant Viscotrol C, new steaming, 4-tolylene diisocyanate and exsiccant soybean residue are evenly mixed, Viscotrol C and 2 wherein, the mol ratio of 4-tolylene diisocyanate is 1: 1, Viscotrol C and 2, the quality sum of 4-tolylene diisocyanate and the mass ratio of soybean residue are 4: 6, and miscellany is through screw rod machine extrusion reaction.Extrusion condition is: respectively be 110,120 and 130 ℃ from the sample introduction to the temperature out.Extruded material in 20MPa, 140 ℃ of following hot pressing 10 minutes, is chilled to and takes out the hot pressing resulting sheet below 50 ℃ on thermocompressor.
The mechanical property of hot pressing composite sheet and water resistance
| Tensile strength (MPa) | Elongation at break (%) | Water tolerance | Water-intake rate (%) * | |
| Embodiment 1 embodiment 2 | 6.41 6.89 | 45.5 100.4 | 0.47 0.55 | 66.7 52.0 |
| Embodiment 3 | 5.16 | 77.98 | 0.42 | 136.66 |
| Embodiment 4 | 5.01 | 131.63 | 0.48 | 126.19 |
| Embodiment 5 | 10.41 | 19.28 | 0.45 | 67.98 |
| Embodiment 6 | 11.73 | 43.61 | 0.46 | 39.88 |
| Embodiment 7 | 14.58 | 31.49 | 0.48 | 34.56 |
| Embodiment 8 | 25.5 | 16.6 | 0.61 | 20.43 |
* water-intake rate: be the rate of body weight gain of sample after in distilled water, soaking 26h under 25 ℃.
Above-mentioned poly-third polyvalent alcohol replaces with other polyether glycol or polyester polyol, and 2,4 toluene diisocyanate replaces obtaining similar result with other vulcabond.
Claims (5)
1. a matrix material is a raw material with soybean residue or the pure and mild vulcabond of soyflour, polyether glycol or polyester polyols, through screw rod machine extrusion reaction, hot-forming obtaining; Wherein the mol ratio of polyether glycol or the pure and mild vulcabond of polyester polyols is 1: 1.5 to 1: 2, and the quality sum of polyether glycol or the pure and mild vulcabond of polyester polyols and the mass ratio of soybean residue or soyflour are 3: 7 to 5: 5.
2. matrix material according to claim 1, it is characterized in that: by polyether glycol or polyester polyol and vulcabond mixed in molar ratio by 1: 1.5 to 1: 2, make the end capped polyurethane prepolymer of isocyano 70～90 ℃ of reactions, mix by the end capped polyurethane prepolymer of isocyano and soybean residue or soyflour mass ratio then by 3: 7 to 5: 5, and through screw rod machine extrusion reaction, hot-forming obtaining.
3. matrix material according to claim 2 is characterized in that: polyurethane prepolymer is all or part of with the end capped prepolymer of isocyano.
4. the preparation method of the described matrix material of claim 1, it is characterized in that: with polyether glycol or polyester polyol and vulcabond mixed in molar ratio by 1: 1.5 to 1: 2, reacted 2～3 hours down at 70～90 ℃, obtain all or part of with the end capped polyurethane prepolymer of isocyano; This polyurethane prepolymer and soybean residue or the soyflour mass ratio by 3: 7 to 5: 5 is mixed, through screw rod machine extrusion reaction, reinstall in the mould 110～140 ℃ hot-forming down, obtain required matrix material.
5. the preparation method of the described matrix material of claim 1 is characterized in that: under 70～90 ℃, simultaneously polyether glycol or polyester polyol mixed with vulcabond, soybean residue or soyflour, and through screw rod machine extrusion reaction, hot-forming obtaining; Wherein the mol ratio of polyether glycol or the pure and mild vulcabond of polyester polyols is 1: 1.5 to 1: 2, and the quality sum of polyether glycol or the pure and mild vulcabond of polyester polyols and the mass ratio of soybean residue or soyflour are 3: 7 to 5: 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031280315A CN1228388C (en) | 2003-05-26 | 2003-05-26 | Composite material and itd preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031280315A CN1228388C (en) | 2003-05-26 | 2003-05-26 | Composite material and itd preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1462770A CN1462770A (en) | 2003-12-24 |
| CN1228388C true CN1228388C (en) | 2005-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB031280315A Expired - Fee Related CN1228388C (en) | 2003-05-26 | 2003-05-26 | Composite material and itd preparation method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308398C (en) * | 2004-05-24 | 2007-04-04 | 武汉大学 | Soya protein plastic with water polyurethane modification and preparing method thereof |
| KR100969041B1 (en) * | 2008-03-25 | 2010-07-09 | 현대자동차주식회사 | Human skin feeling polyurethane artificial leather using non-organic solvent and Preparing method thereof |
| CN101704938B (en) * | 2009-11-27 | 2011-11-30 | 中国科学院青岛生物能源与过程研究所 | Preparation method of bean pulp polyurethane foam plastics |
| TWI750045B (en) * | 2021-02-26 | 2021-12-11 | 南亞塑膠工業股份有限公司 | Pavement laying method |
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