CN105086485A - Multi-component composite material of environmental compatible polyester and plants and preparation method of multi-component composite material - Google Patents
Multi-component composite material of environmental compatible polyester and plants and preparation method of multi-component composite material Download PDFInfo
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Abstract
The invention relates to a multi-component composite material of environmental compatible polyester and plants and a preparation method of the multi-component composite material. The main ingredients of the composite material comprise environmental compatible polyester, plants, an inorganic functional filler and alkyd resin. The preparation method comprises the steps of synthesizing the polyester by virtue of multiple pressure reducing and temperature raising processes, mixing the polyester with the plant raw materials and the inorganic functional filler, performing hot pressing and performing aftertreatment. The environmental compatible polyester contained in the prepared composite material has good degradability, has structural similarity and chemical compatibility with the plant raw materials, additional capacity expansion measures are not needed, the formula of the composite is simplified, and the safety of the composite material is improved. During the preparation process, a step-by-step pressure reduction strategy is adopted, so that the preparation process not only ensures that the reaction energy consumption in the synthesis process is stably reduced, but also is conductive to ensuring the stability of the polymer structure and chemical composition.
Description
Technical field
The present invention relates to a kind of matrix material, belong to environment-friendly material and plant composite material field, particularly the multi-element composite material and preparation method thereof of a kind of Environmental compatibility polyester and plant.
Background technology
Shortage of resources and environmental pollution are two large stumbling-blocks in current economic social development process.Shortage of resources improves the cost of development, environmental pollution damage air resource, water resources, soil resource, and and then compromise the health of people, compromise the achievement of development.In order to alleviate crisis of resource, alleviating environmental pollution, should renewable resources be made full use of, the technique of development environment friendly, resource-conserving and product.Plant resources is a kind of important renewable resources, and the verse of " Not even a prairie fire can destroy the grass, it grows again when the spring breeze blows " is the distinct portrayal of plant resources recyclability.In the history development procedure of economics of underdevelopment in the past, plant resources is fully used, and is used to feed livestock, manufactures baskets craft, manufactures the daily necessities such as mattress, manufactures fertilizer, manufactures the sun-dried mud brick strengthened and to build a house son or be directly used for lid thatched cottage etc.But historical development is to today, " refuse " that the plant resources of valuable source but becomes agriculture production in the past, its purposes is fewer and feweri, often directly burnt in field, pollute air, endanger the healthy of people, affect land and air traffic even brings on a disaster, waste resource again simultaneously.In this case, that develops plant resources utilizes new way, and the utilization ratio improving plant resources has important significance of times.Product based on plant resources is cheap, safe to use due to raw material, has adapted to the pursuit that people are desirable to harmonious co-existence between man and nature, has thus had wide development space.
Be that there are reports in the literature for raw material manufacture matrix material with plant, but often use non-degradable macromolecular material when matrix material manufactures, these materials often derive from oil, natural gas source, be unfavorable on the one hand solving resource and energy shortage problem, lose after discarding in addition and exacerbate white pollution in the environment.Also often the thermoset macromolecule materials such as urea-formaldehyde resin are used when plant composite material manufactures, this kind of macromolecular material is thermoplastic resin raw materials or its solution in the course of processing, hazardous and noxious substances is discharged in the course of processing, and slow releasing hazardous and noxious substances is understood after being processed into product, be unfavorable for that user's is healthy.In order to improve the above-mentioned deficiency of plant composite material, improving the over-all properties of plant composite material simultaneously, this invention exploits the multi-element composite material of a kind of Environmental compatibility polyester and plant, and providing its preparation method.
Summary of the invention
Plant composite material has the feature of resources conservation, environmental protection, is conducive to realizing human social, thus has wide development space.The object of the present invention is to provide and a kind of there is higher Environmental compatibility, excellent combination property, healthy and safe plant composite material and preparation method thereof, with Environmental compatibility polyester and plant for main raw material is made, this matrix material adds the type of plant composite material, enrich the preparation method of plant composite material, widen the Application Areas of plant composite material, enhance the synthetic competitive advantages of plant composite material, improve the share of market of plant composite material.
The present invention is achieved through the following technical solutions: the multi-element composite material of a kind of Environmental compatibility polyester and plant; it is characterized in that: the main component of described matrix material comprises: Environmental compatibility polyester, plant, inorganic functional fillers, Synolac; described Environmental compatibility polyester comprises following structural unit: oxygen propionyl, oxygen ethanoyl, 1.4-butylidene; toluene support, 4; 4`-ditan, oxygen carbonyl imino-; the mass ratio of Environmental compatibility polyester and plant is 0.2:1-1:1, and the mass ratio of inorganic functional fillers and plant is 0.05:1-0.15:1.
Further, in described Environmental compatibility polyester, oxygen ethanoyl is 0.1:1-0.3:1 with the ratio of the amount of substance of oxygen propionyl.
Further, the concrete form of plant is silk sheet or powdered, and inorganic functional fillers is the 1-3 kind in expansile graphite, clay, zinc borate.
Present invention also offers a kind of method preparing the multi-element composite material of above-mentioned Environmental compatibility polyester and plant, comprise the following steps:
(1), weigh lactic acid, oxyacetic acid, BDO, catalyzer join in reactor, stir evenly, then with the air in high pure nitrogen or high-purity argon gas metathesis reactor;
(2), reaction system is decompressed to 1000Pa-5000Pa, then keeps reaction system pressure and is warming up to 90 DEG C of reaction 1h-3h;
(3), reaction system is decompressed to 500Pa-900Pa, then keeps reaction system pressure and is warming up to 130 DEG C of reaction 3h-5h;
(4), reaction system is decompressed to 100Pa-400Pa, then keeps reaction system pressure and is warming up to 170 DEG C of reaction 3h-5h;
(5), reaction system is decompressed to 5Pa-80Pa, and then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 2h-5h;
(6), reaction system is made to return to normal pressure with high pure nitrogen or high-purity argon gas, system temperature is reduced to 80 DEG C-140 DEG C, tolylene diisocyanate, 4 is added under agitation condition, 1-2 kind in 4`-diphenylmethanediisocyanate, tolylene diisocyanate, 4, the quality of 4`-diphenylmethanediisocyanate and with 1, the mass ratio of 4-butyleneglycol is 1.55:1-8.33:1, add inorganic functional fillers, pretreated plant is added after stirring evenly, continue to stir, at 80 DEG C-140 DEG C slaking 5h-15h;
(7), be cooled to room temperature, carry out tearing process, make product become bulk material, then load mould;
(8), at 130 DEG C-170 DEG C, hot pressing 10s-15min under 10MPa-500MPa condition;
(9), cooling and demolding, product surface is cleaned out rear immersion alkyd resin solution, leaching 1min-15min, drain, be dried to constant weight at 30 DEG C-60 DEG C, or after cooling and demolding product surface boring, aperture is 0.1cm-0.3cm, hole density 10-50 hole/100cm
2, clean out rear immersion alkyd resin solution, leaching 1min-15min, drains, is dried to constant weight at 30 DEG C-60 DEG C.
Further, in step (1), described lactic acid can be pure lactic acid, also can be the lactic acid aqueous solution of lactic acid mass content more than 60%, and described catalyzer is the 1-2 kind in the sub-tin of lactic acid, dibutyl tin dilaurate.
Further, in step (1), described oxyacetic acid and the mass ratio of lactic acid are 0.084:1-0.25:1,1, the quality of 4-butyleneglycol and the mass ratio of lactic acid are 0.0024:1-0.024:1, and the quality of catalyzer and the mass ratio of lactic acid are 0.001:1-0.02:1.
Further, in step (6), described plant is the 1-4 kind in beans stalk, beet stalk, rice straw, straw, and described pre-treatment measure is first be cut to short for the raw material of plant the section being less than 10cm, then be dried to constant weight at 40 DEG C-60 DEG C, then carry out stirring and shear 2min-30min.
Further, in step (6), the quality adding plant is 1-5 times of the product quality of step (5), and the quality of inorganic functional fillers and the mass ratio of plant are 0.05:1-0.15:1.
The multi-element composite material of a kind of Environmental compatibility polyester of the present invention and plant, is characterized in that: in the application of the manufacture view of furniture, office appliance, toy, finishing material etc.
Plant composite material of the present invention is a kind of material with polynary moiety, main component comprises Environmental compatibility polyester, plant, inorganic functional fillers, Synolac, the suitable collocation of these compositions both ensure that matrix material had good environment friendly, gave again matrix material with excellent over-all properties simultaneously.In addition, between each composition in plant composite material of the present invention, there is good synergetic property, and agree with mutually with the whole manufacturing process of matrix material, the material phase of technique specified phase is utilized to achieve the well blend of each composition, the specific components that suitable stage adds simultaneously fully solves again the defect in matrix material previous stage, improves the performances such as the intensity of matrix material.In plant composite material of the present invention, Environmental compatibility polyester and plant material have structural similarity, chemical compatibility, without the need to additional coupling agent, simplify the formula of matrix material, improve the security of matrix material.
The present invention employs a kind of novel high polymer material when manufacturing plant composite material, namely a kind of Environmental compatibility polyester is employed, containing diversified structural unit in this Environmental compatibility polyester, comprise oxygen propionyl, oxygen ethanoyl, 1.4-butylidene, toluene supports, 4, 4`-ditan, oxygen carbonyl imino-, the existence of these structural units improves the polymerizing power of monomer on the one hand, be conducive to the Environmental compatibility polyester obtaining high molecular, thus improve the intensity of matrix material, polyester is made to have certain flexibility on the other hand, thus give plant composite material with good snappiness, improve the weather resistance of goods, effectively prevent the damaged in collision in use procedure.The suitable collocation of said structure unit in Environmental compatibility polyester, also the degradation property of combination between polyester and plant material and polyester is optimized, be conducive to the stress reducing composite inner, improve the intensity of matrix material, and be conducive to polymkeric substance use scrap after can fast degradation in the environment, reduce the impact on environment.
The Environmental compatibility polyester that the present invention uses when manufacturing plant composite material has good degradation property in the environment, and the primary product of degraded is lactic acid.Lactic acid is a kind of biochemical, thus itself has good biocompatibility, all can be converted into carbonic acid gas and water, and can be absorbed by plants at human body and occurring in nature, promotes the growth of plant, thus to environment without significant negative impact.Lactic acid can synthesize to chemically, also can be prepared by fermentation method, and fermentation method prepares the main path that lactic acid is lactic acid-producing, and the raw material of fermentation is plant resources, and therefore lactic origin has distinct greenization feature.
The present invention is when manufacturing plant composite material, by the synthesis of polyester, polyester and plant material and inorganic functional fillers mix and hot pressing has been fused into an entirety, have higher production efficiency, the process of decreasing is divided material transfer immediately, transport, is stored and the extra-expense of consumption.In addition, the mixing process of the synthesis of polyester, polyester and plant material and inorganic functional fillers merges by the present invention, two PROCESS COUPLING are a specific stage, both ensure that and easily realized mixing, turn avoid the conversion unit volume problems of too mixing at the very start and cause, reduce fixed investment and power consumption expense.The present invention have employed suitable step-by-step decompression strategy in process of polyester synthesizing, both ensure that the steady of building-up process, reduces the energy consumption in reaction process, is conducive to again ensureing the stable of polymer architecture and chemical constitution.
The present invention is when manufacturing plant composite material, although process from monomer, but the synthesis of polymkeric substance has separated with the hot pressing of mixing raw material, and be polymerized and complete in matrix material preparation process unlike use pre-polymerization resin, so just make having of matrix material higher dimensional, prevent the heat affecting of existence to material of solidification process, improve the production efficiency of material.Before using Synolac, manufacturing processed of the present invention, without the need to an organic solvent, alleviates the pollution in production process, is conducive to the healthy of operator that keep the scene intact; The degraded form of prepared matrix material is mainly hydrolysis, anhydrous, does not substantially degrade, and solves the contradiction between product application and degraded; With an organic solvent less, the residual and harmful volatile pollutent of release, improves the security of goods, is conducive to the healthy of protection user.
Plant composite material of the present invention employs the plant material with extensively source: beans stalk, Rape Straw, rice straw, straw, these plant materials are by products of the maximum farm crop of China's planting scale, raw material sources are abundant, both be conducive to solving the main problem of resource waste of agriculture production, be conducive to again solving the raw material supply problem in plant composite material production process simultaneously.
Have employed pressure sintering in the preparation process of matrix material of the present invention, compared with extrusion molding, production efficiency is higher, operates easier.Matrix material of the present invention can replace partly plastic to use, and alleviates white pollution, alleviates the consumption of petroleum resources; Part timber can be replaced to use, alleviate the soil erosion of denuding and causing.Prepared matrix material can be sheet material, for the manufacture of show and colour etc. in the support section of furniture, container, internal package box, compound foodstuff packing box, interior decoration and finishing material, buildings, also the other products of special-shaped mould version various kinds can be adopted, of many uses.Its use, is conducive to alleviating environmental pollution, and protection people are healthy, improves the environmental consciousness of people.
Embodiment
Embodiment 1
Stand-by after beans stalk, Rape Straw, rice straw, straw are carried out following pre-treatment respectively: the short section being cut to 9cm, under the condition of 60 DEG C, be dried to constant weight, stir and shear 2min.Weighing 167g mass content is the lactic acid aqueous solution of 60%, 8.8g oxyacetic acid, 0.24g1, 4-butyleneglycol, the sub-tin of 0.05g lactic acid, 0.05g dibutyl tin dilaurate joins in reactor, stir evenly, with the air in high pure nitrogen metathesis reactor, reaction system is decompressed to 1000Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 1h, reaction system is decompressed to 500Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 3h, reaction system is decompressed to 100Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 3h, reaction system is decompressed to 5Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 2h, reaction system is made to return to normal pressure with high pure nitrogen, system temperature is reduced to 140 DEG C, 0.15g tolylene diisocyanate is added under agitation condition, 0.222g4, 4`-diphenylmethanediisocyanate, add 6.5g zinc borate, 10g expansile graphite, 5g clay, the pretreated beans stalk of 130g is added after stirring evenly, the pretreated Rape Straw of 100g, the pretreated rice straw of 100g, the pretreated straw of 100g, continue to stir, at 140 DEG C of slaking 5h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 170 DEG C, hot pressing 10s under 500MPa condition, cooling and demolding, product surface is cleaned out rear immersion alkyd resin solution, leaching 1min, drain, constant weight is dried at 60 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 13.9MPa and the multi-element composite material of plant.
Embodiment 2
Stand-by after Rape Straw, rice straw, straw are carried out following pre-treatment respectively: the short section being cut to 1cm, under the condition of 40 DEG C, be dried to constant weight, stir and shear 30min.Weigh 100g lactic acid, 25g oxyacetic acid, 2.4g1, 4-butyleneglycol, the sub-tin of 0.08g lactic acid, 0.02g dibutyl tin dilaurate joins in reactor, stir evenly, with the air in high-purity argon gas metathesis reactor, reaction system is decompressed to 5000Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 3h, reaction system is decompressed to 900Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 5h, reaction system is decompressed to 400Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 5h, reaction system is decompressed to 80Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 5h, reaction system is made to return to normal pressure with high-purity argon gas, system temperature is reduced to 80 DEG C, 10g tolylene diisocyanate is added under agitation condition, 9.8g4, 4`-diphenylmethanediisocyanate, add 6.5g zinc borate, 10g expansile graphite, 5g clay, the pretreated Rape Straw of 50g is added after stirring evenly, the pretreated rice straw of 25g, the pretreated straw of 25g, continue to stir, at 80 DEG C of slaking 15h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 170 DEG C, hot pressing 10s under 500MPa condition, cooling and demolding, product surface is cleaned out rear immersion alkyd resin solution, leaching 1min, drain, constant weight is dried at 60 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 21.2MPa and the multi-element composite material of plant.
Embodiment 3
Stand-by after rice straw, straw are carried out following pre-treatment respectively: the short section being cut to 5cm, under the condition of 50 DEG C, be dried to constant weight, stir and shear 30min.Weighing 111g mass content is the lactic acid aqueous solution of 90%, 12g oxyacetic acid, 1g1, 4-butyleneglycol, the sub-tin of 0.02g lactic acid, 0.08g dibutyl tin dilaurate joins in reactor, stir evenly, with the air in high pure nitrogen metathesis reactor, reaction system is decompressed to 3000Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 2h, reaction system is decompressed to 700Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 4h, reaction system is decompressed to 40Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 3.5h, reaction system is made to return to normal pressure with high pure nitrogen, system temperature is reduced to 100 DEG C, 1.5g tolylene diisocyanate is added under agitation condition, 2.5g4, 4`-diphenylmethanediisocyanate, add 6.5g zinc borate, 10g expansile graphite, 5g clay, the pretreated rice straw of 200g is added after stirring evenly, the pretreated straw of 70g, continue to stir, at 100 DEG C of slaking 10h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 170 DEG C, hot pressing 10s under 500MPa condition, cooling and demolding, product surface is cleaned out rear immersion alkyd resin solution, leaching 1min, drain, constant weight is dried at 60 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 17.4MPa and the multi-element composite material of plant.
Embodiment 4
Stand-by after rice straw is carried out following pre-treatment: the short section being cut to 3cm, under the condition of 45 DEG C, be dried to constant weight, stir and shear 17min.Weigh 100g lactic acid, 9g oxyacetic acid, 0.6g1, 4-butyleneglycol, the sub-tin of 0.5g lactic acid joins in reactor, stir evenly, with the air in high-purity argon gas metathesis reactor, reaction system is decompressed to 2000Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 2h, reaction system is decompressed to 600Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 4h, reaction system is decompressed to 20Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 3h, reaction system is made to return to normal pressure with high-purity argon gas, system temperature is reduced to 120 DEG C, 0.9g4 is added under agitation condition, 4`-diphenylmethanediisocyanate, add 50g clay, the pretreated rice straw of 350g is added after stirring evenly, continue to stir, at 120 DEG C of slaking 8h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 170 DEG C, hot pressing 40s under 500MPa condition, cooling and demolding, product surface is cleaned out rear immersion alkyd resin solution, leaching 1min, drain, constant weight is dried at 50 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 15.8MPa and the multi-element composite material of plant.
Embodiment 5
Stand-by after straw is carried out following pre-treatment: the short section being cut to 0.5cm, under the condition of 45 DEG C, be dried to constant weight, stir and shear 10min.Weighing 125g mass content is the lactic acid aqueous solution of 80%, 10g oxyacetic acid, 0.8g1, 4-butyleneglycol, 2g dibutyl tin dilaurate joins in reactor, stir evenly, with the air in high pure nitrogen metathesis reactor, reaction system is decompressed to 2500Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 3h, reaction system is decompressed to 700Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 4h, reaction system is decompressed to 30Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 4h, reaction system is made to return to normal pressure with high pure nitrogen, system temperature is reduced to 110 DEG C, 0.12g tolylene diisocyanate is added under agitation condition, add 10g zinc borate, 6g expansile graphite, the pretreated straw of 200g is added after stirring evenly, continue to stir, at 110 DEG C of slaking 12h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 170 DEG C, hot pressing 2min under 300MPa condition, cooling and demolding, product surface is cleaned out rear immersion alkyd resin solution, leaching 3min, drain, constant weight is dried at 50 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 18.1MPa and the multi-element composite material of plant.
Embodiment 6
Stand-by after beans stalk, Rape Straw, rice straw, straw are carried out following pre-treatment respectively: the short section being cut to 6cm, under the condition of 55 DEG C, be dried to constant weight, stir and shear 6min.Weighing 111g mass content is the lactic acid aqueous solution of 90%, 8.9g oxyacetic acid, 0.31g1, 4-butyleneglycol, the sub-tin of 0.5g lactic acid, 0.5g dibutyl tin dilaurate joins in reactor, stir evenly, with the air in high pure nitrogen metathesis reactor, reaction system is decompressed to 1000Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 1h, reaction system is decompressed to 500Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 3h, reaction system is decompressed to 100Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 3h, reaction system is decompressed to 5Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 2h, reaction system is made to return to normal pressure with high pure nitrogen, system temperature is reduced to 140 DEG C, 0.3g tolylene diisocyanate is added under agitation condition, 0.2g4, 4`-diphenylmethanediisocyanate, add 15g expansile graphite, 10g clay, the pretreated beans stalk of 100g is added after stirring evenly, the pretreated Rape Straw of 100g, the pretreated rice straw of 100g, the pretreated straw of 50g, continue to stir, at 140 DEG C of slaking 5h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 150 DEG C, hot pressing 8min under 80MPa condition, cooling and demolding, hole at product surface, aperture is 0.3cm, hole density is 10 holes/100cm
2, clean out rear immersion alkyd resin solution, leaching 15min, drain, be dried to constant weight at 60 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 15.4MPa and the multi-element composite material of plant.
Embodiment 7
Stand-by after Rape Straw, rice straw, straw are carried out following pre-treatment respectively: the short section being cut to 1cm, under the condition of 40 DEG C, be dried to constant weight, stir and shear 30min.Weigh 100g lactic acid, 25g oxyacetic acid, 2g1, 4-butyleneglycol, the sub-tin of 0.08g lactic acid, 0.02g dibutyl tin dilaurate joins in reactor, stir evenly, with the air in high-purity argon gas metathesis reactor, reaction system is decompressed to 4000Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 3h, reaction system is decompressed to 800Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 5h, reaction system is decompressed to 400Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 5h, reaction system is decompressed to 70Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 5h, reaction system is made to return to normal pressure with high-purity argon gas, system temperature is reduced to 90 DEG C, 8g tolylene diisocyanate is added under agitation condition, 7g4, 4`-diphenylmethanediisocyanate, add 18g zinc borate, 2g expansile graphite, the pretreated Rape Straw of 200g is added after stirring evenly, the pretreated rice straw of 100g, the pretreated straw of 200g, continue to stir, at 90 DEG C of slaking 15h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 130 DEG C, hot pressing 15min under 10MPa condition, cooling and demolding, hole at product surface, aperture is 0.1cm, hole density is 50 holes/100cm
2, clean out rear immersion alkyd resin solution, leaching 10min, drain, be dried to constant weight at 60 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 16.1MPa and the multi-element composite material of plant.
Embodiment 8
Stand-by after rice straw, straw are carried out following pre-treatment respectively: the short section being cut to 5cm, under the condition of 40 DEG C, be dried to constant weight, stir and shear 20min.Weigh 100g lactic acid, 9g oxyacetic acid, 1g1, 4-butyleneglycol, the sub-tin of 0.1g lactic acid, 0.08g dibutyl tin dilaurate joins in reactor, stir evenly, with the air in high pure nitrogen metathesis reactor, reaction system is decompressed to 3000Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 2h, reaction system is decompressed to 700Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 4h, reaction system is decompressed to 40Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 3.5h, reaction system is made to return to normal pressure with high pure nitrogen, system temperature is reduced to 100 DEG C, 2g tolylene diisocyanate is added under agitation condition, 3g4, 4`-diphenylmethanediisocyanate, add 25g zinc borate, the pretreated rice straw of 180g is added after stirring evenly, the pretreated straw of 70g, continue to stir, at 100 DEG C of slaking 10h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 140 DEG C, hot pressing 8min under 20MPa condition, cooling and demolding, hole at product surface, aperture is 0.2cm, hole density is 20 holes/100cm
2, clean out rear immersion alkyd resin solution, leaching 15min, drain, be dried to constant weight at 50 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 18.2MPa and the multi-element composite material of plant.
Embodiment 9
Stand-by after rice straw is carried out following pre-treatment: the short section being cut to 3cm, under the condition of 45 DEG C, be dried to constant weight, stir and shear 15min.Weighing 125g mass content is the lactic acid aqueous solution of 80%, 15g oxyacetic acid, 0.6g1, 4-butyleneglycol, the sub-tin of 1g lactic acid joins in reactor, stir evenly, with the air in high-purity argon gas metathesis reactor, reaction system is decompressed to 1800Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 2h, reaction system is decompressed to 600Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 4h, reaction system is decompressed to 20Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 3h, reaction system is made to return to normal pressure with high-purity argon gas, system temperature is reduced to 120 DEG C, 1.1g4 is added under agitation condition, 4`-diphenylmethanediisocyanate, add 30g expansile graphite, the pretreated rice straw of 350g is added after stirring evenly, continue to stir, at 120 DEG C of slaking 8h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 160 DEG C, hot pressing 7min under 30MPa condition, cooling and demolding, hole at product surface, aperture is 0.3cm, hole density is 20 holes/100cm
2, clean out rear immersion alkyd resin solution, leaching 12min, drain, be dried to constant weight at 50 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 16.4MPa and the multi-element composite material of plant.
Embodiment 10
Stand-by after straw is carried out following pre-treatment: the short section being cut to 0.5cm, under the condition of 45 DEG C, be dried to constant weight, stir and shear 10min.Weighing 125g mass content is the lactic acid aqueous solution of 80%, 12g oxyacetic acid, 0.8g1, 4-butyleneglycol, 2g dibutyl tin dilaurate joins in reactor, stir evenly, with the air in high pure nitrogen metathesis reactor, reaction system is decompressed to 2500Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 3h, reaction system is decompressed to 700Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 4h, reaction system is decompressed to 30Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 4h, reaction system is made to return to normal pressure with high pure nitrogen, system temperature is reduced to 110 DEG C, 0.12g tolylene diisocyanate is added under agitation condition, add 10g zinc borate, 6g expansile graphite, the pretreated straw of 200g is added after stirring evenly, continue to stir, at 110 DEG C of slaking 12h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 170 DEG C, hot pressing 12min under 10MPa condition, cooling and demolding, hole at product surface, aperture is 0.3cm, hole density is 20 holes/100cm
2, clean out rear immersion alkyd resin solution, leaching 10min, drain, be dried to constant weight at 50 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 20.1MPa and the multi-element composite material of plant.
Embodiment 11
Stand-by after beans stalk is carried out following pre-treatment: the short section being cut to 9cm, under the condition of 60 DEG C, be dried to constant weight, stir and shear 2min.Weighing 143g mass content is the lactic acid aqueous solution of 70%, 9g oxyacetic acid, 0.24g1, 4-butyleneglycol, the sub-tin of 1.5g lactic acid joins in reactor, stir evenly, with the air in high pure nitrogen metathesis reactor, reaction system is decompressed to 1000Pa, then keep reaction system pressure and be warming up to 90 DEG C of reaction 1h, reaction system is decompressed to 500Pa, then keep reaction system pressure and be warming up to 130 DEG C of reaction 3h, reaction system is decompressed to 100Pa, then keep reaction system pressure and be warming up to 170 DEG C of reaction 3h, reaction system is decompressed to 5Pa, then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 2h, reaction system is made to return to normal pressure with high pure nitrogen, system temperature is reduced to 140 DEG C, 0.15g tolylene diisocyanate is added under agitation condition, 0.23g4, 4`-diphenylmethanediisocyanate, add 15g zinc borate, 10g expansile graphite, 5g clay, the pretreated beans stalk of 300g is added after stirring evenly, continue to stir, at 140 DEG C of slaking 5h, be cooled to room temperature, carry out tearing process, product is made to become bulk material, then mould is loaded, at 170 DEG C, hot pressing 3min under 200MPa condition, cooling and demolding, product surface is cleaned out rear immersion alkyd resin solution, leaching 4min, drain, constant weight is dried at 60 DEG C, obtaining tensile strength is the Environmental compatibility polyester of 15.6MPa and the multi-element composite material of plant.
Although the present invention is described in conjunction with above embodiment, but the present invention is not defined to above-described embodiment, and only by the restriction of claims, those of ordinary skill in the art can easily modify to it and change, but do not leave essential idea of the present invention and scope.
Claims (9)
1. the multi-element composite material of an Environmental compatibility polyester and plant; it is characterized in that: the main component of described matrix material comprises: Environmental compatibility polyester, plant, inorganic functional fillers, Synolac; described Environmental compatibility polyester comprises following structural unit: oxygen propionyl, oxygen ethanoyl, 1.4-butylidene; toluene support, 4; 4`-ditan, oxygen carbonyl imino-; the mass ratio of Environmental compatibility polyester and plant is 0.2:1-1:1, and the mass ratio of inorganic functional fillers and plant is 0.05:1-0.15:1.
2. the multi-element composite material of a kind of Environmental compatibility polyester according to claim 1 and plant, is characterized in that: in described Environmental compatibility polyester, oxygen ethanoyl is 0.1:1-0.3:1 with the ratio of the amount of substance of oxygen propionyl.
3. the multi-element composite material of a kind of Environmental compatibility polyester according to claim 1 and plant, is characterized in that: the concrete form of described plant is silk sheet or powdered, and described inorganic functional fillers is the 1-3 kind in expansile graphite, clay, zinc borate.
4. the preparation method of the Environmental compatibility polyester according to the arbitrary claim of claim 1-3 and the multi-element composite material of plant, is characterized in that, comprise the following steps:
(1), weigh lactic acid, oxyacetic acid, BDO, catalyzer join in reactor, stir evenly, then with the air in high pure nitrogen or high-purity argon gas metathesis reactor;
(2), reaction system is decompressed to 1000Pa-5000Pa, then keeps reaction system pressure and is warming up to 90 DEG C of reaction 1h-3h;
(3), reaction system is decompressed to 500Pa-900Pa, then keeps reaction system pressure and is warming up to 130 DEG C of reaction 3h-5h;
(4), reaction system is decompressed to 100Pa-400Pa, then keeps reaction system pressure and is warming up to 170 DEG C of reaction 3h-5h;
(5), reaction system is decompressed to 5Pa-80Pa, and then keeping reaction system pressure and maintaining temperature of reaction is 170 DEG C of reaction 2h-5h;
(6), reaction system is made to return to normal pressure with high pure nitrogen or high-purity argon gas, system temperature is reduced to 80 DEG C-140 DEG C, tolylene diisocyanate, 4 is added under agitation condition, 1-2 kind in 4`-diphenylmethanediisocyanate, tolylene diisocyanate, 4, the quality of 4`-diphenylmethanediisocyanate and with 1, the mass ratio of 4-butyleneglycol is 1.55:1-8.33:1, add inorganic functional fillers, pretreated plant is added after stirring evenly, continue to stir, at 80 DEG C-140 DEG C slaking 5h-15h;
(7), be cooled to room temperature, carry out tearing process, make product become bulk material, then load mould;
(8), at 130 DEG C-170 DEG C, hot pressing 10s-15min under 10MPa-500MPa condition;
(9), cooling and demolding, product surface is cleaned out rear immersion alkyd resin solution, leaching 1min-15min, drain, be dried to constant weight at 30 DEG C-60 DEG C, or after cooling and demolding product surface boring, aperture is 0.1cm-0.3cm, and hole density is 10-50 hole/100cm
2, clean out rear immersion alkyd resin solution, leaching 1m-15min, drains, is dried to constant weight at 30 DEG C-60 DEG C.
5. the preparation method of the multi-element composite material of Environmental compatibility polyester according to claim 4 and plant, it is characterized in that, in step (1), described lactic acid can be pure lactic acid, also can be the lactic acid aqueous solution of lactic acid mass content more than 60%, described catalyzer be the 1-2 kind in the sub-tin of lactic acid, dibutyl tin dilaurate.
6. the preparation method of the multi-element composite material of Environmental compatibility polyester according to claim 4 and plant, it is characterized in that, in step (1), described oxyacetic acid and the mass ratio of lactic acid are 0.084:1-0.25:1,1, the quality of 4-butyleneglycol and the mass ratio of lactic acid are 0.0024:1-0.024:1, and the quality of catalyzer and the mass ratio of lactic acid are 0.001:1-0.02:1.
7. the preparation method of the multi-element composite material of Environmental compatibility polyester according to claim 4 and plant, it is characterized in that, in step (6), described plant is the 1-4 kind in beans stalk, beet stalk, rice straw, straw, described pre-treatment measure is first be cut to short for the raw material of plant the section being less than 10cm, then be dried to constant weight at 40 DEG C-60 DEG C, then carry out stirring and shear 2min-30min.
8. the preparation method of the multi-element composite material of Environmental compatibility polyester according to claim 4 and plant, it is characterized in that, in step (6), the quality adding plant is 1-5 times of the product quality of step (5), and the quality of inorganic functional fillers and the mass ratio of plant are 0.05:1-0.15:1.
9. the Environmental compatibility polyester prepared according to claim 4 and the multi-element composite material of plant, can be used as the raw material of furniture, office appliance, toy, finishing material.
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