CN105086485B - A kind of Environmental compatibility polyester and the multi-element composite material of plant and preparation method thereof - Google Patents
A kind of Environmental compatibility polyester and the multi-element composite material of plant and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of Environmental compatibility polyester and multi-element composite materials of plant and preparation method thereof, the main component of composite material includes Environmental compatibility polyester, plant, inorganic functional fillers, alkyd resin, preparation method includes being synthesized by multiple decompression temperature-rise periods to polyester, the mixing of polyester and plant material and inorganic functional fillers, hot pressing, post-processing step, the Environmental compatibility polyester that the composite material prepared contains has good degradability, there is structural similarity with plant material simultaneously, chemical compatibility, without additional increase-volume measure, simplify the formula of composite material, improve the safety of composite material.Preparation process uses step-by-step decompression strategy, not only ensure that the steady reduction energy consumption of reaction of synthesis process, but also advantageously ensure that the stabilization of polymer architecture and chemical composition.
Description
Technical field
The present invention relates to a kind of composite material, belong to environment-friendly material and plant composite material field, in particular to one
Kind Environmental compatibility polyester and the multi-element composite material of plant and preparation method thereof.
Background technique
Shortage of resources and environmental pollution are two big stumbling-blocks during current economic social development.Shortage of resources improves
The cost of development, environmental pollution damage air resource, water resource, soil resource, and people's health is compromised in turn, it damages
The achievement of development.In order to alleviate crisis of resource, mitigates environmental pollution, renewable resource, exploitation environment friend should be made full use of
Good type, the technique of resource-conserving and product.Plant resources are a kind of important renewable resources, and " prairie fire is burnt endless, and spring breeze is blown
The verse of life again " is the distinct portrayal of plant resources reproducibility.In the history development procedure of past economics of underdevelopment, plant
Goods and materials source is fully used, be used to feed livestock, manufacture baskets craft, manufacture mattress etc. daily necessities, manufacture fertilizer,
Manufacture sun-dried mud brick building of enhancing or be used directly to lid thatched cottage etc..But historical development is to today, is being the plant of valuable source in the past
Goods and materials source but becomes " waste " of agricultural production, and purposes is fewer and fewer, is often directly burnt up in field, polluted sky
Gas endangers the health of people, influences land and air traffic even brings on a disaster, while wasting resource again.At this
In the case of kind, the utilization new way of plant resources is developed, the utilization rate for improving plant resources has important significance of times.It is based on
The product of plant resources has adapted to people and has preferably chased after to harmonious co-existence between man and nature since raw material is cheap, safe to use
It asks, thus there is wide development space.
Manufacturing composite material using plant as raw material, there are reports in the literature, but often makes in composite material manufacture
With non-degradable high molecular material, these materials often derive from petroleum, natural gas resource, be on the one hand unfavorable for solve resource and
Energy shortage problem loses after in addition discarding and exacerbates white pollution in the environment.It also tends to make in plant composite material manufacture
With thermoset macromolecule materials such as Lauxites, this kind of high molecular material is thermoplastic resin raw materials in process or its is molten
Liquid discharges poisonous and harmful substance in process, and will be slow release poisonous and harmful substance after being processed into product, is unfavorable for
The health of user.In order to improve the above-mentioned deficiency of plant composite material, while improving the comprehensive of plant composite material
Can, the present invention develops the multi-element composite material of a kind of Environmental compatibility polyester and plant, and provides preparation method.
Summary of the invention
Plant composite material has the characteristics that resource-effective, environmentally protective, is advantageously implemented human social,
Thus there is wide development space.The purpose of the present invention is to provide one kind to have higher Environmental compatibility, comprehensive performance excellent
Different, healthy and safe plant composite material and preparation method thereof is made using Environmental compatibility polyester and plant by primary raw material, should
Composite material increases the type of plant composite material, enriches the preparation method of plant composite material, it is compound to have widened plant
The application field of material enhances the synthetic competitive advantages of plant composite material, and the market for improving plant composite material is occupied
Rate.
The invention is realized by the following technical scheme: a kind of multi-element composite material of Environmental compatibility polyester and plant,
Be characterized in that: the main component of the composite material includes: Environmental compatibility polyester, plant, inorganic functional fillers, alkyd tree
Rouge, the Environmental compatibility polyester include following structural unit: oxygen propiono, oxygen acetyl group, 1.4- butylidene, toluene support,
The mass ratio of 4,4`- diphenyl methanes, oxygen carbonyl imino group, Environmental compatibility polyester and plant is 0.2:1-1:1, inorganic functional
The mass ratio of filler and plant is 0.05:1-0.15:1.
Further, the ratio between amount of substance of oxygen acetyl group and oxygen propiono is 0.1 in the Environmental compatibility polyester:
1-0.3:1。
Further, the specific form of plant be silk piece or powdered, inorganic functional fillers be expansile graphite, clay,
1-3 kind in zinc borate.
The present invention also provides a kind of method of multi-element composite material for preparing above-mentioned Environmental compatibility polyester and plant, packets
Include the following steps:
(1), lactic acid, glycolic, 1,4-butanediol, catalyst are weighed to be added in reactor, stirs evenly, then uses High Purity Nitrogen
Air in gas 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 reactions
1h-3h；
(3), reaction system is decompressed to 500Pa-900Pa, then keeps reaction system pressure and is warming up to 130 DEG C of reactions
3h-5h；
(4), reaction system is decompressed to 100Pa-400Pa, then keeps reaction system pressure and is warming up to 170 DEG C of reactions
3h-5h；
(5), reaction system is decompressed to 5Pa-80Pa, then keeps reaction system pressure and maintaining reaction temperature is 170 DEG C
React 2h-5h；
(6), restore reaction system to normal pressure with high pure nitrogen or high-purity argon gas, system temperature is reduced to 80 DEG C -140
DEG C, toluene di-isocyanate(TDI), the 1-2 kind in 4,4`- methyl diphenylene diisocyanate, toluene diisocyanate are added under stirring condition
Acid esters, the quality of 4,4`- methyl diphenylene diisocyanate and be 1.55:1-8.33:1 with the mass ratio of 1,4-butanediol,
Inorganic functional fillers are added, pretreated plant is added after stirring evenly, continues to stir evenly, in 80 DEG C of -140 DEG C of curing 5h-
15h；
(7), it is cooled to room temperature, carries out tearing processing, product is made to become bulk material, be then charged into mold；
(8), hot pressing 10s-15min under the conditions of 130 DEG C -170 DEG C, 10MPa-500MPa；
(9), cooling and demolding immerses alkyd resin solution after cleaning out product surface, soak 1 min -15min, drip
It is dry, it drills after 30 DEG C of -60 DEG C of dryings to constant weight or cooling and demolding in product surface, aperture is 0.1 cm -0.3cm, Kong Mi
Spend the hole 10-50/100cm2, alkyd resin solution is immersed after cleaning out, and is soaked 1 min -15min, is drained, at 30 DEG C -60 DEG C
It dries to constant weight.
Further, in step (1), the lactic acid can be pure lactic acid, be also possible to lactic acid mass content 60%
Above lactic acid aqueous solution, the catalyst are lactic acid stannous, the 1-2 kind in dibutyl tin dilaurate.
Further, in step (1), the mass ratio of the glycolic and lactic acid be 0.084:1-0.25:1,1,
The quality of 4- butanediol and the mass ratio of lactic acid are 0.0024:1-0.024:1, the quality of catalyst and the mass ratio of lactic acid
For 0.001:1-0.02:1.
Further, in step (6), the plant is beans stalk, beet stalk, rice straw, the 1-4 kind in straw, described
Pretreatment measure be that first the raw material of plant is chopped as the section less than 10cm, then in 40 DEG C of -60 DEG C of dryings to constant weight, then
It is stirred 2 min -30min of shearing.
Further, in step (6), the quality that plant is added is 1-5 times of product quality of step (5), inorganic function
The quality of energy filler 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 and plant of the invention, it is characterised in that: in furniture, office
The application of the manufacture view of articles, toy, ornament materials etc..
Plant composite material of the invention is a kind of material with polynary constituent, and main component includes that environment is compatible
Property polyester, plant, inorganic functional fillers, alkyd resin, it is good that the suitable collocation of these ingredients both ensure that composite material had
Environment friendly, while again assign composite material with excellent comprehensive performance.In addition, each in plant composite material of the present invention
There is good concertedness between ingredient, and mutually agree with the entire manufacturing process of composite material, utilize technique moment
Material phase realizes the good mixing of each ingredient, while the specific components that suitable stage is added sufficiently solve previous stage again
The defects of composite material improves the performances such as the intensity of composite material.Environmental compatibility in plant composite material of the invention
Polyester and plant material have structural similarity, chemical compatibility, are not necessarily to additional coupling agent, simplify the formula of composite material,
Improve the safety of composite material.
The present invention has used a kind of novel high polymer substance when manufacturing plant composite material, that is, has used a kind of environment phase
Capacitive polyester contains diversified structural unit, including oxygen propiono, oxygen acetyl group, 1.4- in this Environmental compatibility polyester
On the one hand the presence of butylidene, toluene support, 4,4`- diphenyl methane, oxygen carbonyl imino group, these structural units improves monomer
On the other hand polymerizing power, the Environmental compatibility polyester for being conducive to obtain high molecular weight make to improve the intensity of composite material
Obtaining polyester, there is certain flexibility to improve the durability of product to assign plant composite material with good flexibility, have
Effect prevents the damaged in collision in use process.The suitable collocation of above structure unit, also optimizes poly- in Environmental compatibility polyester
The degradability of combination and polyester between ester and plant material is conducive to the stress for reducing composite inner, improves composite wood
The intensity of material, and be conducive to after polymer use is scrapped can fast degradation in the environment, reduce the influence to environment.
The present invention used Environmental compatibility polyester when manufacturing plant composite material has good drop in the environment
Xie Xing, the primary product of degradation are lactic acid.Lactic acid is a kind of biochemical, thus itself has good bio-compatible
Property, it can be converted into carbon dioxide and water in human body and nature, and can be absorbed by plants, promote the growth of plant,
Thus to environment without significant negative impact.Lactic acid can also be prepared, fermentation method by being chemically synthesized by fermentation method
The main path that lactic acid is production of lactic acid is prepared, the raw material of fermentation is plant resources, therefore lactic origin has distinct green
Change feature.
The present invention is when manufacturing plant composite material, by the synthesis of polyester, polyester and plant material and inorganic functional fillers
Mixing and hot pressing be fused into an entirety, production efficiency with higher, reduce process it is discrete when material transfer, fortune
Defeated, storage and consumption extra charge.In addition, the present invention is by the synthesis of polyester, polyester and plant material and inorganic functional fillers
Mixed process fusion, two PROCESS COUPLINGs a specific stage, both ensure that it is easy to accomplish be uniformly mixed, in turn avoid
Consersion unit volume problems of too, reduces fixed investment and power consumption expense caused by mixing at the very start.The present invention exists
Suitable step-by-step decompression strategy is used in process of polyester synthesizing, both ensure that the steady of synthesis process, and had been reduced reaction process
In energy consumption, and advantageously ensure that the stabilization of polymer architecture and chemical composition.
The present invention is when manufacturing plant composite material, although being processed since monomer, the synthesis of polymer and mixed
The hot pressing for closing raw material separates, and rather than using pre-polymerization resin to polymerize like that is completed in composite material preparation process
, it is higher dimensional that having for composite material is allowed in this way, it is therefore prevented that heat affecting of the presence of solidification process to material mentions
The high production efficiency of material.Before applying alkyd resin, manufacturing process of the invention alleviates life without using organic solvent
Pollution during production, the health for the operator that is conducive to keep the scene intact；The degradation form master of prepared composite material
It to be hydrolysis, it is anhydrous then substantially non-degradable, solve the contradiction between product application and degradation；It is less to use organic solvent, no
Residual and the harmful volatile pollutant of release, improve the safety of product, are conducive to the health for protecting user.
Plant composite material of the invention has used the plant material with extensive source: beans stalk, Rape Straw, rice straw, wheat
Stalk, these plant materials are the by-products of the maximum crops of China's planting scale, and raw material sources are abundant, not only improve solution agriculture
Industry produces main problem of resource waste, while the raw material supply advantageously accounted in plant composite material production process again is asked
Topic,.
Pressure sintering is used in the preparation process of composite material of the present invention, compared with extrusion molding, production efficiency is more
Height operates easier.Composite material of the present invention can replace partly plastic to use, and mitigate white pollution, mitigate petroleum money
The consumption in source；It can replace the use of part timber, mitigate soil erosion caused by the denudation.Prepared composite material can be with
Plate, for furniture, container, internal package box, the support section of compound foodstuff packing box, interior decoration and ornament materials,
The manufacture of show and colour etc. in building can also use the other products of special-shaped mould version various kinds, widely used.It
Use, be conducive to mitigate environmental pollution, protect people's health, improve the environmental consciousness of people.
Specific embodiment
Embodiment 1
It is stand-by after beans stalk, Rape Straw, rice straw, straw are pre-processed as follows respectively: to be chopped as the section of 9cm, at 60 DEG C
Under conditions of dry to constant weight, stirring shearing 2min.Weigh lactic acid aqueous solution, the 8.8 g ethyl alcohol that 167g mass content is 60%
Acid, 0.24g 1,4-butanediol, 0.05g lactic acid stannous, 0.05g dibutyl tin dilaurate are added in reactor, stir evenly, and use
Air in high pure nitrogen metathesis reactor, reaction system are decompressed to 1000Pa, then keep reaction system pressure and are warming up to
90 DEG C of reaction 1h, reaction system are decompressed to 500Pa, then keep reaction system pressure and are warming up to 130 DEG C of reaction 3h, reactant
System is decompressed to 100Pa, then keeps reaction system pressure and is warming up to 170 DEG C of reaction 3h, reaction system is decompressed to 5Pa, then
It keeps reaction system pressure and maintaining reaction temperature is 170 DEG C of reaction 2h, restore reaction system to normal pressure with high pure nitrogen, it will
System temperature is reduced to 140 DEG C, and 0.15g toluene di-isocyanate(TDI), 0.222g 4,4`- diphenyl methane two are added under stirring condition
6.5g zinc borate, 10g expansile graphite, 5g clay is added in isocyanates, and the pretreated beans stalk of 130g, 100g are added after stirring evenly
The pretreated rice straw of pretreated Rape Straw, 100g, the pretreated straw of 100g, continue to stir evenly, in 140 DEG C of curing 5h,
It is cooled to room temperature, carries out tearing processing, product is made to become bulk material, be then charged into mold, under the conditions of 170 DEG C, 500MPa
Hot pressing 10s, cooling and demolding immerse alkyd resin solution after cleaning out product surface, soak 1 min, drain, in 60 DEG C of dryings
To constant weight, the multi-element composite material of Environmental compatibility polyester and plant that tensile strength is 13.9 MPa is obtained.
Embodiment 2
It is stand-by after Rape Straw, rice straw, straw are pre-processed as follows respectively: to be chopped as the section of 1cm, in 40 DEG C of condition
30 min are sheared in lower drying to constant weight, stirring.Weigh 100g lactic acid, 25 g glycolics, 2.4g 1,4-butanediol, 0.08g cream
Sour stannous, 0.02g dibutyl tin dilaurate are added in reactor, are stirred evenly, with the air in high-purity argon gas metathesis reactor,
Reaction system is decompressed to 5000Pa, then keeps reaction system pressure and is warming up to 90 DEG C of reaction 3h, reaction system is decompressed to
Then 900Pa keeps reaction system pressure and is warming up to 130 DEG C of reaction 5h, reaction system is decompressed to 400Pa, then keeps anti-
It answers system pressure and is warming up to 170 DEG C of reaction 5h, reaction system is decompressed to 80Pa, then keeps reaction system pressure and remains anti-
Answering temperature is 170 DEG C of reaction 5h, restores reaction system to normal pressure with high-purity argon gas, system temperature is reduced to 80 DEG C, stirring bar
10g toluene di-isocyanate(TDI), 9.8g 4 are added under part, it is swollen that 6.5g zinc borate, 10g is added in 4`- methyl diphenylene diisocyanate
The pretreated Rape Straw of 50g, the pretreated rice straw of 25g, the pretreated straw of 25g is added in swollen property graphite, 5g clay after stirring evenly,
Continue to stir evenly, in 80 DEG C of curing 15h, is cooled to room temperature, carries out tearing processing, so that product is become bulk material, then fill
Enter mold, hot pressing 10s under the conditions of 170 DEG C, 500MPa, cooling and demolding immerses alkyd resin after cleaning out product surface
Solution soaks 1 min, drains, dry to constant weight at 60 DEG C, obtains the Environmental compatibility polyester and plant that tensile strength is 21.2 MPa
The multi-element composite material of object.
Embodiment 3
It is stand-by after rice straw, straw are pre-processed as follows respectively: it is chopped as the section of 5cm, drying under conditions of 50 DEG C
To constant weight, 30 min of stirring shearing.Weigh lactic acid aqueous solution, the 12 g glycolics, 1g 1,4- fourth that 111g mass content is 90%
Glycol, 0.02g lactic acid stannous, 0.08g dibutyl tin dilaurate are added in reactor, stir evenly, and are replaced with high pure nitrogen anti-
The air in device is answered, reaction system is decompressed to 3000Pa, then keeps reaction system pressure and is warming up to 90 DEG C of reaction 2h, reacts
System is decompressed to 700Pa, then keeps reaction system pressure and is warming up to 130 DEG C of reaction 4h, and reaction system is decompressed to 300Pa,
Then it keeps reaction system pressure and is warming up to 170 DEG C of reaction 4h, reaction system is decompressed to 40Pa, then keeps reaction system pressure
Strong and maintaining reaction temperature is 170 DEG C of reaction 3.5h, restores reaction system to normal pressure with high pure nitrogen, system temperature is reduced to
100 DEG C, 1.5g toluene di-isocyanate(TDI), 2.5g 4 are added under stirring condition, 4`- methyl diphenylene diisocyanate is added
The pretreated rice straw of 200g, the pretreated straw of 70g is added in 6.5g zinc borate, 10g expansile graphite, 5g clay after stirring evenly, after
It is continuous to stir evenly, in 100 DEG C of curing 10h, it is cooled to room temperature, carries out tearing processing, product is made to become bulk material, be then charged into
It is molten to immerse alkyd resin for mold, hot pressing 10s under the conditions of 170 DEG C, 500MPa, cooling and demolding after cleaning out product surface
Liquid soaks 1 min, drains, dry to constant weight at 60 DEG C, obtains the Environmental compatibility polyester and plant that tensile strength is 17.4MPa
Multi-element composite material.
Embodiment 4
Rice straw is carried out stand-by after pre-processing as follows: being chopped as the section of 3cm, dry under conditions of 45 DEG C to constant weight, stir
Mix 17 min of shearing.100g lactic acid, 9 g glycolics, 0.6g 1,4-butanediol are weighed, 0.5g lactic acid stannous is added to reactor
In, it stirs evenly, with the air in high-purity argon gas metathesis reactor, reaction system is decompressed to 2000Pa, then keeps reaction system pressure
By force and 90 DEG C of reaction 2h are warming up to, reaction system is decompressed to 600Pa, then keeps reaction system pressure and is warming up to 130 DEG C instead
4h is answered, reaction system is decompressed to 300Pa, and it then keeps reaction system pressure and is warming up to 170 DEG C of reaction 4h, reaction system decompression
To 20Pa, then keeps reaction system pressure and maintaining reaction temperature is 170 DEG C of reaction 3h, keep reaction system extensive with high-purity argon gas
Again to normal pressure, system temperature is reduced to 120 DEG C, 0.9g 4 is added under stirring condition, 4`- methyl diphenylene diisocyanate adds
Enter 50g clay, the pretreated rice straw of 350g is added after stirring evenly, continues to stir evenly, in 120 DEG C of curing 8h, be cooled to room temperature, into
Row tearing processing, makes product become bulk material, is then charged into mold, hot pressing 40s under the conditions of 170 DEG C, 500MPa, cooling de-
Mould immerses alkyd resin solution after cleaning out product surface, soak 1 min, drain, dry to constant weight at 50 DEG C, is drawn
Stretch the multi-element composite material of Environmental compatibility polyester and plant that intensity is 15.8MPa.
Embodiment 5
Straw is carried out stand-by after pre-processing as follows: being chopped as the section of 0.5cm, dry under conditions of 45 DEG C to constant weight,
10 min of stirring shearing.Lactic acid aqueous solution, the 10g glycolic, 0.8g 1,4-butanediol that 125g mass content is 80% are weighed,
2g dibutyl tin dilaurate is added in reactor, is stirred evenly, and with the air in high pure nitrogen metathesis reactor, reaction system subtracts
It is depressed into 2500Pa, then keep reaction system pressure and is warming up to 90 DEG C of reaction 3h, reaction system is decompressed to 700Pa, then protects
It holds reaction system pressure and is warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keeps reaction system pressure simultaneously
170 DEG C of reaction 4h are warming up to, reaction system is decompressed to 30Pa, then keeps reaction system pressure and maintaining reaction temperature is 170
DEG C reaction 4h, restore reaction system to normal pressure with high pure nitrogen, system temperature be reduced to 110 DEG C, is added under stirring condition
10g zinc borate, 6g expansile graphite is added in 0.12g toluene di-isocyanate(TDI), and the pretreated straw of 200g is added after stirring evenly, after
It is continuous to stir evenly, in 110 DEG C of curing 12h, it is cooled to room temperature, carries out tearing processing, product is made to become bulk material, be then charged into
Mold, 2 min of hot pressing, cooling and demolding immerse alkyd resin after cleaning out product surface under the conditions of 170 DEG C, 300MPa
Solution soaks 3 min, drains, dry to constant weight at 50 DEG C, obtains the Environmental compatibility polyester and plant that tensile strength is 18.1MPa
The multi-element composite material of object.
Embodiment 6
It is stand-by after beans stalk, Rape Straw, rice straw, straw are pre-processed as follows respectively: to be chopped as the section of 6cm, at 55 DEG C
Under conditions of dry to constant weight, 6 min of stirring shearing.Weigh lactic acid aqueous solution, the 8.9 g ethyl alcohol that 111g mass content is 90%
Acid, 0.31g 1,4-butanediol, 0.5g lactic acid stannous, 0.5g dibutyl tin dilaurate are added in reactor, stir evenly, with height
Air in pure nitrogen gas metathesis reactor, reaction system are decompressed to 1000Pa, then keep reaction system pressure and are warming up to 90
DEG C reaction 1h, reaction system is decompressed to 500Pa, then keeps reaction system pressure and is warming up to 130 DEG C of reaction 3h, reaction system
It is decompressed to 100Pa, then keep reaction system pressure and is warming up to 170 DEG C of reaction 3h, reaction system is decompressed to 5Pa, then protects
Holding reaction system pressure and maintaining reaction temperature is 170 DEG C of reaction 2h, restores reaction system to normal pressure with high pure nitrogen, by body
It is that temperature is reduced to 140 DEG C, 0.3g toluene di-isocyanate(TDI), 0.2g 4,4`- diphenylmethane diisocyanate is added under stirring condition
15g expansile graphite, 10g clay is added in ester, be added after stirring evenly the pretreated beans stalk of 100g, the pretreated Rape Straw of 100g,
The pretreated rice straw of 100g, the pretreated straw of 50g, continue to stir evenly, and in 140 DEG C of curing 5h, are cooled to room temperature, are torn
Processing is split, product is made to become bulk material, is then charged into mold, 8 min of hot pressing under the conditions of 150 DEG C, 80MPa, cooling and demolding,
It drills in product surface, aperture 0.3cm, hole density is 10 holes/100cm2, alkyd resin solution is immersed after cleaning out, and is soaked
15 min, drain, dry to constant weight at 60 DEG C, obtain the more of Environmental compatibility polyester that tensile strength is 15.4 MPa and plant
First composite material.
Embodiment 7
It is stand-by after Rape Straw, rice straw, straw are pre-processed as follows respectively: to be chopped as the section of 1cm, in 40 DEG C of condition
30 min are sheared in lower drying to constant weight, stirring.Weigh 100g lactic acid, 25 g glycolics, 2g 1,4-butanediol, 0.08g lactic acid
Stannous, 0.02g dibutyl tin dilaurate are added in reactor, are stirred evenly, with the air in high-purity argon gas metathesis reactor, instead
It answers system to be decompressed to 4000Pa, then keep reaction system pressure and is warming up to 90 DEG C of reaction 3h, reaction system is decompressed to
Then 800Pa keeps reaction system pressure and is warming up to 130 DEG C of reaction 5h, reaction system is decompressed to 400Pa, then keeps anti-
It answers system pressure and is warming up to 170 DEG C of reaction 5h, reaction system is decompressed to 70Pa, then keeps reaction system pressure and remains anti-
Answering temperature is 170 DEG C of reaction 5h, restores reaction system to normal pressure with high-purity argon gas, system temperature is reduced to 90 DEG C, stirring bar
8g toluene di-isocyanate(TDI), 7g 4 are added under part, 18g zinc borate, 2g dilatancy is added in 4`- methyl diphenylene diisocyanate
Graphite is added the pretreated Rape Straw of 200g, the pretreated rice straw of 100g, the pretreated straw of 200g, continues to stir after stirring evenly
Uniformly, it in 90 DEG C of curing 15h, is cooled to room temperature, carries out tearing processing, product is made to become bulk material, be then charged into mold,
130 DEG C, 15 min of hot pressing under the conditions of 10MPa, cooling and demolding drill in product surface, aperture 0.1cm, hole density be 50 holes/
100cm2, alkyd resin solution is immersed after cleaning out, and is soaked 10 min, is drained, it is dry to constant weight at 60 DEG C, obtain tensile strength
For the Environmental compatibility polyester of 16.1 MPa and the multi-element composite material of plant.
Embodiment 8
It is stand-by after rice straw, straw are pre-processed as follows respectively: it is chopped as the section of 5cm, drying under conditions of 40 DEG C
To constant weight, 20 min of stirring shearing.Weighing 100g lactic acid, 9 g glycolics, 1g 1,4-butanediol, 0.1g lactic acid stannous,
0.08g dibutyl tin dilaurate is added in reactor, is stirred evenly, with the air in high pure nitrogen metathesis reactor, reactant
System is decompressed to 3000Pa, then keeps reaction system pressure and is warming up to 90 DEG C of reaction 2h, reaction system is decompressed to 700Pa, so
Reaction system pressure is kept afterwards and is warming up to 130 DEG C of reaction 4h, and reaction system is decompressed to 300Pa, then keeps reaction system pressure
By force and 170 DEG C of reaction 4h are warming up to, reaction system is decompressed to 40Pa, then keeps reaction system pressure and maintaining reaction temperature is
170 DEG C of reaction 3.5h, restore reaction system to normal pressure with high pure nitrogen, system temperature are reduced to 100 DEG C, add under stirring condition
Enter 2g toluene di-isocyanate(TDI), 3g 4,4`- methyl diphenylene diisocyanate is added 25g zinc borate, 180g is added after stirring evenly
The pretreated straw of pretreated rice straw, 70g, continues to stir evenly, and in 100 DEG C of curing 10h, is cooled to room temperature, is torn
Processing, makes product become bulk material, is then charged into mold, 8 min of hot pressing under the conditions of 140 DEG C, 20MPa, cooling and demolding,
Product surface drilling, aperture 0.2cm, hole density are 20 holes/100cm2, alkyd resin solution, leaching 15 are immersed after cleaning out
Min is drained, dry to constant weight at 50 DEG C, obtains the polynary of Environmental compatibility polyester that tensile strength is 18.2 MPa and plant
Composite material.
Embodiment 9
Rice straw is carried out stand-by after pre-processing as follows: being chopped as the section of 3cm, dry under conditions of 45 DEG C to constant weight, stir
Mix 15 min of shearing.Weigh lactic acid aqueous solution, the 15 g glycolics, 0.6g 1,4-butanediol that 125g mass content is 80%, 1g
Lactic acid stannous is added in reactor, is stirred evenly, and with the air in high-purity argon gas metathesis reactor, reaction system is decompressed to
Then 1800Pa keeps reaction system pressure and is warming up to 90 DEG C of reaction 2h, reaction system is decompressed to 600Pa, then keeps anti-
It answers system pressure and is warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keeps reaction system pressure and heats up
To 170 DEG C of reaction 4h, reaction system is decompressed to 20Pa, then keeps reaction system pressure and maintaining reaction temperature is 170 DEG C anti-
3h is answered, restores reaction system to normal pressure with high-purity argon gas, system temperature is reduced to 120 DEG C, 1.1g 4 is added under stirring condition,
30g expansile graphite is added in 4`- methyl diphenylene diisocyanate, and the pretreated rice straw of 350g is added after stirring evenly, continues to stir
Uniformly, it in 120 DEG C of curing 8h, is cooled to room temperature, carries out tearing processing, product is made to become bulk material, be then charged into mold,
160 DEG C, 7 min of hot pressing under the conditions of 30MPa, cooling and demolding drill in product surface, aperture 0.3cm, hole density be 20 holes/
100cm2, alkyd resin solution is immersed after cleaning out, and is soaked 12 min, is drained, it is dry to constant weight at 50 DEG C, obtain tensile strength
For the Environmental compatibility polyester of 16.4 MPa and the multi-element composite material of plant.
Embodiment 10
Straw is carried out stand-by after pre-processing as follows: being chopped as the section of 0.5cm, dry under conditions of 45 DEG C to constant weight,
10 min of stirring shearing.Lactic acid aqueous solution, the 12g glycolic, 0.8g 1,4-butanediol that 125g mass content is 80% are weighed,
2g dibutyl tin dilaurate is added in reactor, is stirred evenly, and with the air in high pure nitrogen metathesis reactor, reaction system subtracts
It is depressed into 2500Pa, then keep reaction system pressure and is warming up to 90 DEG C of reaction 3h, reaction system is decompressed to 700Pa, then protects
It holds reaction system pressure and is warming up to 130 DEG C of reaction 4h, reaction system is decompressed to 300Pa, then keeps reaction system pressure simultaneously
170 DEG C of reaction 4h are warming up to, reaction system is decompressed to 30Pa, then keeps reaction system pressure and maintaining reaction temperature is 170
DEG C reaction 4h, restore reaction system to normal pressure with high pure nitrogen, system temperature be reduced to 110 DEG C, is added under stirring condition
10g zinc borate, 6g expansile graphite is added in 0.12g toluene di-isocyanate(TDI), and the pretreated straw of 200g is added after stirring evenly, after
It is continuous to stir evenly, in 110 DEG C of curing 12h, it is cooled to room temperature, carries out tearing processing, product is made to become bulk material, be then charged into
Mold, 12 min of hot pressing under the conditions of 170 DEG C, 10MPa, cooling and demolding drill in product surface, aperture 0.3cm, hole density
For 20 holes/100cm2, alkyd resin solution is immersed after cleaning out, and is soaked 10 min, is drained, it is dry to constant weight at 50 DEG C, it obtains
Tensile strength is the Environmental compatibility polyester of 20.1MPa and the multi-element composite material of plant.
Embodiment 11
Beans stalk is carried out stand-by after pre-processing as follows: being chopped as the section of 9cm, dry under conditions of 60 DEG C to constant weight, stir
Mix 2 min of shearing.Lactic acid aqueous solution, the 9 g glycolics, 0.24g 1,4-butanediol that 143g mass content is 70% are weighed,
1.5g lactic acid stannous is added in reactor, is stirred evenly, and with the air in high pure nitrogen metathesis reactor, reaction system is decompressed to
Then 1000Pa keeps reaction system pressure and is warming up to 90 DEG C of reaction 1h, reaction system is decompressed to 500Pa, then keeps anti-
It answers system pressure and is warming up to 130 DEG C of reaction 3h, reaction system is decompressed to 100Pa, then keeps reaction system pressure and heats up
To 170 DEG C of reaction 3h, reaction system is decompressed to 5Pa, then keeps reaction system pressure and maintaining reaction temperature is 170 DEG C of reactions
2h, restores reaction system to normal pressure with high pure nitrogen, and system temperature is reduced to 140 DEG C, and 0.15g toluene is added under stirring condition
It is viscous that 15g zinc borate, 10g expansile graphite, 5g is added in diisocyanate, 0.23g 4,4`- methyl diphenylene diisocyanate
Soil is added the pretreated beans stalk of 300g, continues to stir evenly, in 140 DEG C of curing 5h, be cooled to room temperature, torn after stirring evenly
Processing, makes product become bulk material, is then charged into mold, 3 min of hot pressing under the conditions of 170 DEG C, 200MPa, cooling and demolding,
Alkyd resin solution is immersed after product surface is cleaned out, and is soaked 4 min, is drained, it is dry to constant weight at 60 DEG C, it obtains stretching strong
Degree is the Environmental compatibility polyester of 15.6 MPa and the multi-element composite material of plant.
Although present invention combination above embodiments are described, the present invention is not limited to above-described embodiment,
And be only defined by the appended claims, those of ordinary skill in the art easily can modify and change to it, but simultaneously
Without departing from essential idea and range of the invention.
Claims (4)
1. the preparation method of a kind of Environmental compatibility polyester and the multi-element composite material of plant, which is characterized in that including following step
It is rapid:
(1), weigh lactic acid, glycolic, 1,4-butanediol, catalyst are added in reactor, stir evenly, then with high pure nitrogen or
Air in high-purity argon gas metathesis reactor；The mass ratio of the glycolic and lactic acid is 0.084:1-0.25:1, Isosorbide-5-Nitrae-
The quality of butanediol and the mass ratio of lactic acid are 0.0024:1-0.024:1, and the quality of catalyst and the mass ratio of lactic acid are
0.001:1-0.02:1；
(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, then keeps reaction system pressure and maintaining reaction temperature is 170 DEG C of reactions
2h-5h；
(6), restore reaction system to normal pressure with high pure nitrogen or high-purity argon gas, system temperature is reduced to 80 DEG C -140 DEG C, is stirred
Toluene di-isocyanate(TDI), the 1-2 kind in 4,4`- methyl diphenylene diisocyanate are added under the conditions of mixing, reaction obtains environment phase
Capacitive polyester, wherein toluene di-isocyanate(TDI), 4,4`- methyl diphenylene diisocyanate quality and with 1,4-butanediol
Mass ratio is 1.55:1-8.33:1, and inorganic functional fillers are added, pretreated silk sheet plant is added after stirring evenly, and is continued
It stirs evenly, the quality that plant is added is 1-5 times of Environmental compatibility polyester quality, the quality of inorganic functional fillers and plant
Mass ratio is 0.05:1-0.15:1, in 80 DEG C of -140 DEG C of curing 5h-15h；The inorganic functional fillers be expansile graphite,
1-3 kind in clay, zinc borate；
(7), it is cooled to room temperature, carries out tearing processing, product is made to become bulk material, be then charged into mold；
(8), hot pressing 10s-15min under the conditions of 130 DEG C -170 DEG C, 10MPa-500MPa；
(9), cooling and demolding immerses alkyd resin solution after cleaning out product surface, soak 1min-15min, drain, 30
It drills after DEG C -60 DEG C of dryings to constant weight or cooling and demolding in product surface, aperture 0.1cm-0.3cm, hole density 10-50
Hole/100cm2, alkyd resin solution is immersed after cleaning out, and is soaked 1-15min, is drained, in 30 DEG C of -60 DEG C of dryings to constant weight.
2. the preparation method of Environmental compatibility polyester according to claim 1 and the multi-element composite material of plant, feature
It is, in step (1), the lactic acid can be pure lactic acid, be also possible to lactic acid of the lactic acid mass content 60% or more
Aqueous solution, the catalyst are lactic acid stannous, the 1-2 kind in dibutyl tin dilaurate.
3. the preparation method of Environmental compatibility polyester according to claim 1 and the multi-element composite material of plant, feature
It is, in step (6), the plant is beans stalk, beet stalk, rice straw, the 1-4 kind in straw, the pretreatment measure
For first the raw material of plant is chopped as the section less than 10cm, shearing is then then stirred to constant weight in 40 DEG C of -60 DEG C of dryings
2min-30min。
4. the multiple elements design material of a kind of Environmental compatibility polyester and plant that the method according to claim 1 is prepared
Material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101020780A (en) * | 2007-03-15 | 2007-08-22 | 上海交通大学 | Prepn process of polylactic acid-base thermoplastic wood-plastic composite material |
| CN101747644A (en) * | 2008-12-16 | 2010-06-23 | 金发科技股份有限公司 | Plant powder modified thermoplastic wood-plastic composite and preparation method and application |
| CN103819801A (en) * | 2014-03-13 | 2014-05-28 | 福建师范大学 | Polyolefin wood-plastic composite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020780A (en) * | 2007-03-15 | 2007-08-22 | 上海交通大学 | Prepn process of polylactic acid-base thermoplastic wood-plastic composite material |
| CN101747644A (en) * | 2008-12-16 | 2010-06-23 | 金发科技股份有限公司 | Plant powder modified thermoplastic wood-plastic composite and preparation method and application |
| CN103819801A (en) * | 2014-03-13 | 2014-05-28 | 福建师范大学 | Polyolefin wood-plastic composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 聚乳酸-乙醇酸共聚物的降解性能研究;张诚;《中国优秀硕士学位论文全文数据库(电子期刊) 医药卫生科技辑》;20130515;E080-3 |
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