CN102753611A - Compositions containing plant matter and synthetic fibres and method for preparing such compositions - Google Patents

Abstract

The present invention relates to a composition containing plant matter and synthetic fibres, characterised in that said composition includes: at least 10 wt% and at most 95 wt% of a thermoplastic composition (a) including at least one polyolefin and at least one thermoplastic starch; and at least 5 wt% and at most 90 wt% of synthetic fibres (b) having a diameter of 2 to 35 microns and a specific modulus of 25 to 230 GPa.m3/kg.

Description

The method that comprises the compsn of phyteral and synthon and be used to prepare this based composition

The present invention relates to multiple novel composition, they comprise a kind of based on polyolefine and based on the thermoplastic compounds of plastifying starch (a) and synthon (b).The invention still further relates to a kind of these method for compositions that are used to prepare.

Be interpreted as being meant reversible ground, softening under the heat effect and a kind of compsn of hardened when cooling off at " thermoplastic compounds " among the present invention.It presents at least one " glass transition " temperature (T _g), be in frangible vitreous state at the pars amorpha of the following said composition of this temperature, and possibly stand the reversible viscous deformation in the above said composition of this temperature.Of the present invention based on the second-order transition temperature of Thermoplasticity of Starch compsn or at least one of these second-order transition temperatures preferably between-120 ° of C and 150 ° of C.This thermoplastic compounds has represented a kind of ability through being formed in the conventional process of using of the industry that is used for transforming plastics, fabric, timber, and these processes are for example extruded, injection molding, molded, roational molding, hot compacting, blow molding, spinning, calendering or compacting.Its viscosity of under the temperature of 100 ° of C to 200 ° of C, measuring is 10 and 10 generally ⁶Between the Pa.s.

Preferably, said compsn is " hot melt " compsn, that is to say that it can apply high shear (promptly through these melting materials are flowed simply or it is suppressed simply) and be formed.Its viscosity of under the temperature of 100 ° of C to 200 ° of C, measuring is 10 and 10 generally ³Between the Pa.s.

In implication of the present invention; Term " synthon " is interpreted as being meant a kind of compsn that obtains through the material forming (especially after fusion or pyrolysis) with a kind of mineral, fossil or organic origin, provides the fiber with 2 to 35 micron diameters and variable-length with this.These synthon preferably show 25 and 230GPa.m ³High specific modulus between the/kg, and specifically be silicious (spun glass), based on (PET, PBT, PS, PP, PA, PLA, PU or the Kevlar) of (thomel), metallic (steel or aluminum fiber) or the synthesized polymer properties of the character of carbon.Therefore can relate to inorganic fibre and organic fibre.This definition does not in fact comprise vegetable fibre, that is to say in nature, specifically is the fiber that in plant, exists.

Thisly obtain conventional plastics and (be also referred to as petroleum-based plastics current; Opposite with biological plastics based on renewable resources) oil and gas reserves day by day rare; Because Greenhouse effect and Global warming have caused the weather interference; Require to seek Sustainable development with more natural, more clean, public opinion state more healthy, recyclable, the effective product of the energy more; And under the overall background of these environment that in rules and tax system, change and economy; Necessary is that the operational multiple novel composition that obtains from renewable resources will be arranged, these compsns be simultaneously competitive, just be designed to only to have seldom or have no to the negative impact of environment and be effectively same with material technically from beginning from the conventional parent material preparation of fossil sources.

Under this spirit, the contriver has explored different approach recent decades, comprise the material of introducing biogenetic derivation as in the petroleum-based plastics resin, and the reinforce in polyolefine especially.These materials have been showed following advantage: the cost with low is relatively made very on a large scale; Represented the favourable relatively ecosystem characterization aspect environment; Can not produced toxic gas (for example opposite) by burning, and be callable in industry with PVC.

Under this background; At the fortifier of selecting to be used for the petroleum-based plastics resin, carried out with vegetable fibre particularly as flax and hemp fibre, cereal straw fiber, kenaf, wood fibre or cellulosic fibre (regenerated fiber) be attached to the petroleum-based plastics resin, particularly like many researchs relevant in the Vestolen PP 7052.The mixture of natural fiber or the product of mixture have been obtained to be commonly referred to thus.Paper below this for example can quote: " the interface alternation effect in the fibre-reinforced thermoplastic compound (Interfacial Interactions in Fiber Reinforced Thermoplastic Composites) "; Author L í via D á ny á di, Hungary AS, material and environmental chemistry chemical research center; Budapest technology and economic university; Physical chemistry and Department of Materials Science, plastics and rubber technology laboratory, 2009.

This married operation is grasped in today well, but from improving the purpose of producing with these mixture characteristics, many researchs are still underway.Yet, consider that these vegetable fibres generally are that be rich in very much water and very hydrophilic, and resin is anhydrous basically and hydrophobic in essence, it is not easy introducing this type vegetable fibre.In fact, the synthetic product that generally is the oil source being incorporated between resin and the vegetable fibre as dispersion agent, expanding material and/or coupling agent is standing procedure.In addition, the problem that in the petroleum-based plastics resin, combines vegetable fibre to run into is the height unstable that is being used to change and is handling vegetable fibre under normal temps and the shearing condition of these petroleum-based plastics resins.This is because even in the presence of specified stabiliser, vegetable fibre is still very responsive to shearing action, heat, light and mikrobe.In addition, the dehydration of these fibers or dry has promoted it is attached in the resin or itself and the consistency of resin, and this is accompanied by must losing of its enhancing ability.In fact, even through introduce surpassing 40% amount, the enhancing that replaces the desired resin mechanical property that spun glass causes through for example introduced plant fiber is still not enough usually so that it can be fit to many application.

Other researchs have related to the vegetable fibre that these are identical and have been attached in the resin of biogenetic derivation, particularly like polylactic acid-based (PLA).Therefore obtained to be called as the multiple compsn of biological composite, so for satisfying the standard of widely applying, these compsns show even the more insufficient and more not satisfied characteristic than the mixture of petroleum-based plastics and vegetable fibre.

In fact; Applicant company has been observed and has been had a kind of needs to obtaining operational novel composition; These compsns in fact shown with thermo-mechanical property like the synthon enhanced petroleum-based plastics resene, have improved characteristic really even with respect to the latter, and use the renewable resources of maximum on the short-term meaning simultaneously; Like starch, and reduced simultaneously to be used to make, to transport, to change and in fact reclaimed the required energy of these compsns in addition.After repeatedly attempting; Applicant company is found; The diverse a kind of new way of the approach of being followed in the research of preferably following and carrying out for many years prepares the mixture based on renewable resources; These mixtures have high tensile modulus, high modulus in flexure and high resistance to impact shock; This is through from following principle, that is: preferably use the thermoplastic compounds of a kind of biogenetic derivation that is fit to this requirement and the synthon with very high specific modulus, rather than keep with vegetable fibre or biogenetic derivation weighting agent enhanced polyolefine.

The present invention has introduced for a kind of novelty of problem set forth above and favourable solution; This is through the novel composition based on vegetable material and synthon is provided, these compsns show with market on the enhanced polyolefin resin be suitable mechanical characteristics at least.

Say that more properly according to the present invention, these compsns based on vegetable material and synthon comprise:

A kind of thermoplastic compounds (a) of at least 10% and maximum by weight 95% by weight, said composition comprises at least a polyolefine and at least a thermoplastic starch, and

At least 5% and maximum by weight 90% synthon (b) by weight, these fibers have the diameter between 2 and 35 microns and have at 25GPa.m ³/ kg and 230GPa.m ³Specific modulus between the/kg.

This is because applicant company is astonishing and unexpectedly find many researchs after, uses specific thermoplastic compounds (a) rather than only comprises that polyolefinic compsn makes it to obtain equivalent, in fact even better mechanical characteristics on the contrary with all expections.Do not hope to be subject to any theory; Applicant company is believed; To the adhesivity of these fibers and the consistency of this type of mixture, this thermoplastic starch performance is as a kind of expanding material or coupling agent between thermoplastic compounds (a) and synthon (b) through influence.

In addition; Applicant company can be found; With polyolefin; Specifically be with respect to glass or thomel, this thermoplastic compounds (a) has shown excellent interaction characteristic and with respect to the adhesivity of synthon, makes this thermoplastic compounds (a) oneself to form a kind of adhesive composite by it fully like this or is used for the compsn of these synthon of adhesive bond (b).

In implication of the present invention; " thermoplastic starch " is interpreted as being meant a kind of state; Starch no longer is to be in graininess under this state; That is to say that its present a kind of state no longer is a semi-crystalline state particulate state, and this be it in the stored tissue and organ of higher plant, specifically be the seed at grain, fabaceous seed, yam stem tuber or cassava, root, bulb, do or fruit in natural present characteristic state.This natural miocrystalline state comes down to because the macromole of pulullan (one of two kinds of staples of starch).Under this native state, starch granules demonstrates from 15% to 45% and the percent crystallinity that changes, and this depends on the plant origin of starch in fact and depends on any processing that it is stood.Crystal granular starch is placed under the polarized light and presents a kind of distinctive cross at microscopically, is called as Maltese cross, and this is the typicalness of crystalline particulate form.About crystal granular starch is explained in more detail; Can be referring to the works " Initiation à la chimie et à la physico-chimie macromol é culaires " [Polymer Chemistry and Physics the rudiments of chemistry (Introduction to macromolecular chemistry and physical chemistry)] of S.Perez; First version in 2000; The 13rd volume; The the 41st to 86 page; The chapter 2 of Groupe

d ' Etudes et d ' Applications des Polymeres [French polymkeric substance research and application group], title is " Structure et morphologie du grain d ' amidon " [structure of starch small grain and a form].The Thermoplasticity of Starch state be through be generally with respect to granular starch 15% and 35% between the combination water and/or the suitable softening agent of content boil/plasticising granular starch and through providing mechanical energy and heat energy to obtain.Patent US 5 from Warner Lambert; 095,054 and described the thermoplasticity state (having crystallinity that reduce or disappearance) of this sex change and the means that are used to obtain this type of thermoplastic starch especially owing to having added softening agent from EP 0 497 706 B1 of applicant company.In order to obtain amorphous thermoplastic starch; The distortion of this hemicrystalline natural particulate form of starch can be carried out through thermomechanical or extrusion in a kind of medium with low relatively hydration; But require a kind of existence of softening agent in this case, otherwise the danger that makes starch carbonizing is just arranged.

Be known that; The combination of polyolefine and thermoplastic starch makes might obtain multiple thermoplastic compounds, and its characteristic can be regulated through the type of selecting starch, character, plasticising ratio, linkage heat plastic starch and polyolefinic degree and the hybrid technique of softening agent.Mode by way of example; Can mention people's such as Rodriguez-Gonzalez paper " high-performance LDPE/ thermoplastic starch blend: " to pure poly a kind of continuable surrogate (High performance LDPE/thermoplastic starch blends:a sustainable alternative to pure polyethylene); Polymkeric substance; 44 (2003), the 1517-1526 page or leaf.

Significant development has in recent years made it and might obtain at the thermoplastic compounds that shows the novelty of good mechanical properties aspect rigidity, toughness and the resistance to impact shock through developing novel technology, like those of the theme of the patented claim WO 2009/095617, WO 2009/095618 and the WO 2009/095622 that form applicant company.Yet this type comprise that the compsn of starch and a kind of non-starchiness polymkeric substance does not show and be fit to the desired characteristic of following material applications, demanding deflection of these material applications or tensile modulus, good temperature performance characteristic or high resistance to impact shock.

In addition,, add these reagent, generally be attended by the reduction on the resistance to impact shock from the purpose of improving its deflection and stretched mechanical characteristic though might toughener be attached in the polyolefin-based compsn.For example, applicant company has been found that in based on thermoplastic starch and polyolefinic compsn and to add the reduction that clay or lime carbonate have caused the improvement of deflection mechanical characteristics and has been attended by resistance to impact shock.

Applicant company has been found that; Through to adding specific synthon (b), might improve the deflection of this compsn and the resistance to impact shock that the stretched mechanical characteristic has unexpectedly significantly improved these compsns simultaneously based on thermoplastic starch with in as polyolefinic a kind of compsn of non-starchiness polymkeric substance.

Existing people describes based on polyolefine, starch and other components compsn of (specifically comprise synthon and more properly say it is spun glass).

This is the situation from the patented claim WO 2009/022195 of Cereplast; This application has been described the compound of polyolefine and starch, and these compounds can comprise that very usually (from a lot of inventory of mentioned additive) spun glass is as toughener.In this document, do not provide the specific embodiment of this based composition, more do not provide the characteristic that this based composition possibly have.In addition, this starch is by adding a kind of PEG as expanding material, being introduced into wherein as the weighting agent that is dispersed in the polyolefine with a kind of (non-thermal plasticity) particulate form.

Similarly, file US 2006/0194902 A1 has described a kind of compsn, and said composition comprises a kind of polyolefine, a kind of expanding material and a kind of non-thermal plasticity starch filled dose.This compsn can randomly comprise a spot of spun glass or cellulosic fibre.

Patent EP 1 265 967 has described the thermoplastic starch powder compsn, and these compsns comprise the weighting agent that is in the inorganic particle form, like lime carbonate, and perhaps pine tree vegetable fibre, and another kind of alternatively polymkeric substance.It can be (in a lot of product inventory of imagining) a kind of polyolefine that the latter is described to.There is not the corresponding to compsn of description or proposition and the present invention in this document.

Patent US 6,231, and 970 B1 have described the compsn based on thermoplastic starch and a kind of specific weighting agent.In addition, this compsn can comprise fiber or a kind of other polymkeric substance alternatively.

Compsn based on vegetable material and synthon according to the present invention is characterised in that, it advantageously with can be through compacting, hot compacting, extrude, the form of particle, chip, sheet material, sheet material, powder or fiber mat that calendering, spinning, injection molding or air blowing form provides.

According to ISO 1183 methods, the density that compsn according to the present invention advantageously represents is between 1.1 and 2.5, preferably between 1.15 and 2.10 and more preferably between 1.3 and 2.00.It is quite high that this density is actually, but from the angle of density metal and even the angle of market a large amount of synthetic polymers that exist, that prepare with inorganic filler see and remain highly favourable.

In addition, owing to must there be thermoplastic starch, be biogenetic derivation at least in part according to compsn of the present invention.However, it has represented outstanding hot mechanical features and has formed a kind of favourable material of a kind of height that is suitable for numerous Application Areass, like prime mover industry, aircraft industry, shipping industry or building industry.Say that more properly it shows:

According to ISO 527 methods, very high tensile modulus, usually greater than about 2500MPa, and better still greater than 3000MPa,

According to ISO 178 methods, equally very high and greater than 1500MPa, be preferably greater than 3000MPa and still better greater than the modulus in flexure of 5000MPa,

And outstanding resistance to impact shock, promptly surpass about 25kJ/m usually at 23 ° of C according to ISO 179/IeU method ², in fact even 30kJ/m ²Non-notch Xia Erpi impact value (unnotched Charpy impact value), perhaps surpass about 15kJ/m usually at 23 ° of C according to ISO 179/IeA method ², in fact even 20kJ/m ²Jagged Xia Erpi impact value (notched Charpy impact value).

Compsn according to the present invention comprises: at first, a kind of specific thermoplastic compounds (a), said composition shows the relatively low advantage of density and shows the density of measuring according to ISO 1183 methods is 1.05 and 1.25 and preferably between 1.1 and 1.2.This thermoplastic compounds (a) must comprise a kind of polyolefine.This polyolefine can be a virgin material, that is to say before do not have used, though can be through adding additive or preparing through mixing.It can be recycling also, that is to say to be derived from value-added polyolefine part or object through salvage material.

This polyolefine preferentially is selected from high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), straight-chain low density polyethylene, HPP homopolymer polypropylene (PPHs), Atactic Polypropelene (RPPs), polypropylene copolymer (PPcs) and polybutylenes, also has their any blend.

This polyolefine specifically can be the blend of polyolefins, and at least a in these polyolefine can be carried silane, vinylformic acid or maleic anhydride unit, below is called functional unit.Preferably, the scope of silane, vinylformic acid or the unitary amount of maleic anhydride be load bearing unit the polyolefine gross weight from 0.1% to 10%.Particularly, can consider polyolefins with maleic anhydride graft.

According to an embodiment; The unitary polyolefine of not bearing function that this polyolefine comprises is from 10% to 90% by weight, in fact even by weight from 25% to 75%, and the unitary polyolefine of bearing function is from 10% to 90% by weight, in fact even by weight from 25% to 75%.

Advantageously, the weight-average molecular weight that this polyolefine appears is 8500 and 10,000, between 000 dalton, particularly 15,000 and 1,000, between 000 dalton.

The polyolefine of this composition is semi-crystalline state preferably.So at least one in its fusing point is advantageously between 100 ° of C and the 200 ° of C, preferably between 110 ° of C and 170 ° of C.Fusing point can be measured with 10 ° of heating of plastic of C/ minute through differential scanning calorimetry (DSC) in the known manner: this measurement can be through being heated to sample up to 200 ° of C for the first time; Be cooled to the temperature of-50 ° of C; Then sample is heated for the second time; Measure fusing point in the second time in the heat-processed, heating and cooling speed be 10 ° C/ minute.

Preferably; The polyolefine of this thermoplastic compounds (a) is following a kind of polymkeric substance; It is with respect to all carbon that in said polymkeric substance, exists, comprised at least 50%, preferred 70%, specifically greater than the carbon of renewable sources 80% and still better 100%, on standard A STM D 6852 and/or standard A STMD 6866 meanings.Reason for this reason, thermoplastic compounds (a) can comprise at least a that obtain from the biogenetic derivation monomer, specifically be the polyolefine that the functionalized grafts from bio-ethanol or biological methanol or biogenetic derivation obtains.

This thermoplastic compounds (a) also must comprise a kind of thermoplastic starch.This starch preferably has and is lower than 15%, preferably is lower than 5% and more preferably less than 1% percent crystallinity, that is to say, and be to be in amorphous basically state.

This percent crystallinity specifically can be measured through X-ray diffraction, as described in patent US 5,362,777 (the 9th hurdle, the 8th to 24 row).

This thermoplastic starch does not advantageously demonstrate the starch granules of Maltese cross (this is a kind of characteristic that shows that the crystalline granular starch exists) basically through polarizing microscope.

Thermoplastic compounds (a) has preferably included at least a thermoplastic starch; This thermoplastic starch by dry weight basis be this thermoplastic compounds (a) greater than 25%, be preferably greater than 35%, more preferably greater than 50%, this thermoplastic compounds (a) is a kind of polyolefine or multiple polyolefinic blend to 100% rest part basically.Usually, this polyolefine has formed the successive disperse phase of this thermoplastic compounds (a), and thermoplastic starch has formed discontinuous disperse phase.

Employed starch preferentially is selected from granular starch, water soluble starch and organically-modified starch in the preparation of this thermoplastic starch compositions.

According to a kind of first alternative form, be a kind of granular starch for the selected starch of the preparation of thermoplastic starch.Through a kind of hot treat mechanically and/or carry out close blend with a kind of suitable softening agent can be so that the crystallinity of said granular starch be lower than 15%.Said granular starch can be any plant origin.It can be natural cereal, like the starch of wheat, corn, barley, triticale, chinese sorghum or rice; Stem tuber is like the starch of yam or cassava; Or leguminous plants, like the starch of pea and soybean; Or on the contrary, otherwise from these plants, obtain, rich in amylose or be rich in the starch of pulullan (wax); And any mixture of above-mentioned starch.This granular starch can also be the granular starch through the means modification of physics, chemistry and/or enzyme.It can be granular starch or a kind of white dextrin of any fluidization or oxidation.But it can also be to have carried out physical and chemical modified the granular starch that can keep the structure of initial native starch; Like starch esterification and/or etherificate, the starch through grafting, acetylize, hydroxypropylation, anionization, cationization, crosslinked, phosphatization, succinylation and/or silylanization modification particularly.At last, it can be combination and a kind of starch of modification or any mixture of this type of granular starch through processing set forth above.

In a preferred embodiment, this crystal granular starch is to be selected from native starch, fluidization starch, Sumstar 190, to have stood any mixture of a kind of starch of chemical modification, white paste and these products.

This granular starch is a kind of particle verivate of a grow wheat or pea granular starch or wheat or pea starch preferably.It generally show by weight less than 5% under 20 ° of C in demineralized water the content of soluble material and can be largely insoluble in cold water.

According to one second alternative form; For the selected starch of the preparation of thermoplastic starch is a kind of water soluble starch; It can also derive from any plant origin, otherwise comprises that a kind of rich in amylose perhaps is rich in the water soluble starch of pulullan (wax).This soluble starch can be used as the substituting and introduce partially or completely to this granular starch.

In implication of the present invention, " water soluble starch " is interpreted as being meant under 20 ° of C and after under the mechanical stirring 24 hours, and a soluble part is by weight and equals any starch deutero-polysaccharide material of 5% at least in demineralized water.This soluble fractions is preferably by weight greater than 20% and particularly by weight greater than 50%.Certainly, this Zulkovsky starch can be (soluble fractions=100%) that is dissolved in fully in the demineralized water.

This water soluble starch uses with solid form, preferred anhydrous basically solid form, that is to say be not dissolving or be dispersed in a kind of water or organically in the solvent.Therefore the explanation that importantly runs through is not after this obscured term " can be water-soluble " with term " dissolved " mutually.

This type of water soluble starch can be through pregelatinized, pregelatinized, starch suspension on forcing machine in rotary drum or solution atomizing, use that non-solvent precipitates, hydro-thermal boiling, chemistry functional or obtain through another kind of technology.It specifically is a kind of starch pregelatinised, that extrude or atomizing, a kind of dextrin of high-degree of conversion (being also referred to as yellow starch gum), a kind of maltodextrin, a kind of mixture of a kind of starch of functionalization or these products.

These pregelatinised starch can be through carrying out the processing of hydro-thermal gelationization to native starch or treated starch; Particularly through steam boiling, the boiling of jet-type pulp digester, in boiling on the rotary drum, boiling in kneader/extruder system; And carry out drying then; For example in baking oven, at fluidized-bed with warm air, on rotary drum, through the atomizing, through extruding or obtaining through lyophilize.This kind of starch demonstrate generally under 20 ° of C in demineralized water greater than 5% and more at large the solubleness between 10% to 100% and less than 15%, generally be less than 5% and more often be less than 1%, certain or even starch crystals degree of zero.By way of example, can mention by applicant company manufacturing and the product under

trade(brand)name, sold.

The dextrin of high-degree of conversion can be prepared through the dextrinization of in a kind of anhydrous relatively acidic medium, carrying out by the starch of natural or modification.They specifically can be the white dextrin or the yellow starch gum of solubility.By way of example, can mention product

053 or

072 by applicant company manufacturing and sale.This type of dextrin demonstrates under 20 ° of C in demineralized water the solubleness between 10% and 95% generally and less than 15% and generally less than 5% starch crystals degree.

These maltodextrins can obtain through the hydrolytic action of acidity, oxidation or the enzyme of starch in a kind of aqueous medium.Particularly, they can have between 0.5 and 40, preferably at the dextrose equivalent between 0.5 and 12 (DE) better between 0.5 and 20 and still.This type of maltodextrin for example be the applicant company manufacturing and sell down in trade(brand)name

and under 20 ° of C, in demineralized water, demonstrate generally greater than 90%, really or even near 100% solubleness, and generally less than the starch crystals degree of 5% (and almost nil usually).

The starch of these functionalization can be obtained by a kind of starch natural or modification.This multifunction for example can be given its solubleness in water to sufficiently high degree through esterification or etherificate and obtained.The soluble fractions of starch appeared the as above definition of this type of functionalization is greater than 5%, be preferably greater than 10%, still better greater than 50%.

This functionalization particularly can through in the acetylizing of aqueous phase and diacetyl oxide or mixed acid anhydride, in the hydroxypropylation effect of viscosity in mutually, doing mutually or the cationization effect of viscosity in mutually, be used for acquisition through the anionization of doing mutually or phosphorization or the succinylation effect of viscosity in mutually carried out.The starch of these water-soluble height functionalization can be presented between 0.01 to 3 substitution value and still better between 0.05 and 1.Preferably, the reactant that is used for this starch is carried out modification or functionalization has reproducible source.

According to another favourable alternative form, this water soluble starch is the water soluble starch of a grow wheat or pea or a kind of water-soluble verivate of wheat or pea starch.

It has advantageously presented a kind of low water content, this be generally less than by weight 10%, preferably less than by weight 5%, particularly less than by weight 2% and ideally less than by weight 0.5%, really even less than by weight 0.2%.

According to one the 3rd alternative form; For the selected starch of the preparation of thermoplastic starch is a kind of organically-modified starch; Preferred a kind of organic soluble starch, it can also derive from any plant origin, comprises a kind of organically-modified starch; Preferred a kind of organic soluble starch, on the contrary rich in amylose perhaps is rich in pulullan (wax).This organic soluble starch can be used as for granular starch or for the substituting and introduce partially or completely of water soluble starch.

In implication of the present invention, any starch deutero-polysaccharide material outside the granular starch of the definition that " organically-modified starch " provides on being interpreted as being meant and digging up the roots according to this or the water soluble starch.Preferably, this organically-modified starch almost is unbodied, that is to say the starch crystals degree that appears less than 5%, is the starch crystals degree less than 1% and particularly zero generally.It it is further preferred that " organic soluble "; That is to say that in a kind of solvent demonstrating (under 20 ° of C) equals 5% a soluble part by weight at least, this solvent is selected from the methyl ester class of ethanol, ETHYLE ACETATE, propyl acetate, butylacetate, diethyl carbonate, propylene carbonate, Methyl glutarate, triethyl citrate, dibasic ester class, methyl-sulphoxide (DMSO), isosorbide dimethyl ether, vanay, diacetic acid Coronex, two oleic acid Coronexs and vegetables oil.This soluble fractions is preferably by weight greater than 20% and particularly by weight greater than 50%.Certainly, this organic soluble starch can be (soluble fractions=100%) that dissolves in fully in above one or more solvents of pointing out.

This organically-modified starch can be according to the present invention with solid form, preferably use with anhydrous basically form.Preferably, its water-content be generally less than by weight 10%, preferably less than by weight 5%, particularly less than by weight 2% and ideally less than by weight 0.5%, really even less than by weight 0.2%.

The organically-modified starch that can in compsn according to the present invention, use can be through natural or modification starch (as set forth above those) the height functionalization be used for preparation.The effect of this height functionalization can for example be through esterification or etherificate to sufficiently high level so that its be unbodied basically or give its insoluble in water and preferably the solvability in above organic solvent carry out.The soluble fractions of starch appeared the as above definition of this type of functionalization is greater than 5%, be preferably greater than 10%, still better greater than 50%.

The effect of this height functionalization particularly can be through carrying out acetylize with diacetyl oxide in solvent phase; The acid anhydrides of grafting (for example in solvent phase or through reactivity, extruding) acid or the oligopolymer of mixed acid anhydride, lipid acid acyl chlorides, caprolactone or rac-Lactide; At the hydroxypropylation of viscosity in mutually and crosslinked; Doing mutually or the cationization of viscosity in mutually and crosslinked; The anionization that carries out through phosphatization or succinylation and doing mutually or viscosity crosslinked in mutually, silylanization, the telomerization of carrying out with divinyl obtains.Starch of these organically-modified, preferred organic soluble height functionalization can be the fatty ester of the aliphatic chain with 4 to 22 carbon of acetic ester or these starch materials (starch, dextrin, maltodextrin) of starch, dextrin or maltodextrin particularly, and the substitution value (DS) that these bonded products preferably demonstrate is 0.5 and 3.0, between preferred 0.8 and 2.8 and particularly between 1.0 and 2.7.

For example, they can be capronate, octanoate, decylate, laurate, cetylate, oleic acid ester and the stearate of starch, dextrin or maltodextrin, particularly present the DS between 0.8 and 2.8.

According to another favourable alternative form, this organically-modified starch is the organically-modified starch of a grow wheat or pea or a kind of organically-modified verivate of wheat or pea starch.

Preferably, this thermoplastic compounds (a) comprises a kind of softening agent.

" softening agent " be interpreted as being meant any lower molecular weight, that is to say preferably have the organic molecule that is less than 5000 molecular weight; When it being combined in this thermoplastic compounds (a) or the thermoplastic starch through the hot treat mechanically under the temperature between 20 ° of C and 200 ° of C, this organic molecule caused this thermoplastic compounds (a) or thermoplastic starch second-order transition temperature reduction and/or cause the crystallinity of this starch to reduce up to making it reach an amorphous basically state.

The plasticizer loading that thermoplastic compounds (a) preferably shows by dry weight basis be this thermoplastic compounds (a) 4% and 50% between, preferably between 8% and 40% and particularly between 15% and 25%.

Water is the most natural softening agent for starch, and therefore adopts water usually, but other molecules also are highly effective, specifically are carbohydrates, like the mixture of glucose, SANMALT-S, sucrose or fructose, polyvalent alcohol and these products.

In the context of the present invention; This softening agent preferentially is selected from di-alcohols, ternary alcohols and polyalcohols, like the mixture of glycerine, poly-glycerol, Isosorbide, sorbitanic class, Sorbitol Powder, N.F,USP MANNITOL and hydrogenant glucose syrup, organic acid salt such as Sodium.alpha.-hydroxypropionate, urea and these products.So the molar mass that this softening agent advantageously appears is less than 5000, preferably less than 1000 and especially preferably less than 400.This softening agent preferably has greater than 18 and equals 380 molar mass at most, and in other words it does not preferably comprise water.

Very specifically when starch is organically-modified starch; The softening agent of this starch can be selected from methyl, ethyl or the fatty ester class of organic acid such as lactic acid, Hydrocerol A, succsinic acid, hexanodioic acid and pentanedioic acid, the acetate esters or the fatty ester class of perhaps single alcohol, glycol, trivalent alcohol or polyvalent alcohol such as ethanol, Diethylene Glycol, glycerine and Sorbitol Powder.By way of example; Can mention: the ester class of glyceryl diacetate (glyceryl diacetate), triacetin (vanay), Isosorbide diacetate esters, two sad Coronexs, two oleic acid Coronexs, two LAURIC ACID 99 MIN Coronexs, dicarboxylicacid or dibasic ester class (DBE), and the mixture of these products.

This softening agent; Outside preferably dewatering, the ratio that in this thermoplastic starch, exists generally is in being to be by 25 to 120 parts of dry weight basis in 10 to 120 parts of dry weight basis and preferred especially ratio in 1 to 150 part of dry weight basis, preferred ratio in the per 100 parts starch of dry weight basis.

Therefore; According to a favourable alternative form, in this thermoplastic starch, exist preferably dewater outside softening agent be to be in the per 100 parts starch of dry weight basis in the ratio of 25 to 110 parts of dry weight basis, preferably in the ratio of 30 to 100 parts of dry weight basis and particularly in the ratio of 30 to 90 parts of dry weight basis.

This thermoplastic compounds (a) preferably includes at least a plastifying starch that obtains from and the following as thermoplastic starch: any mixture of fatty ester, dextrin, maltodextrin and these products of the aliphatic chain of the starch of native starch, pregelatinized starch, extrusioning starch, atomizing starch, fluidization starch, Sumstar 190, cationic starch, anionic starch, hydroxyalkylation, cross-linking starch, starch acetate, starch and 4 to 22 carbon, they carry out plasticising through at least one item in the above softening agent of listing.

In addition, this thermoplastic compounds (a) advantageously comprises:

From 25% to 85% thermoplastic starch by weight,

From 10% to 60% polyolefine by weight,

From 4% to 40% at least a softening agent by weight, outside preferably dewatering,

And more preferably:

From 35% to 85% thermoplastic starch by weight, for example from 35% to 80%,

From 10% to 50% polyolefine by weight,

And from 10% to 30% at least a softening agent by weight, outside preferably dewatering.

Also preferably include a kind of coupling agent according to compsn of the present invention.

" coupling agent " should be understood that to be meant any organic molecule of the functional group that has at least two free or shelter in the present invention, and these functional groups can react with the molecule that carries the functional group with active hydrogen (like the softening agent of starch or starch).This coupling agent can join in the said composition with make it might with at least a portion of this softening agent through covalent linkage be connected on this starch, in fact even also to this polyolefine, if particularly the latter has been carried functional group.

Therefore; This coupling agent can for example be selected from the compound that has at least two identical or different and free or functional groups of sheltering, and these functional groups are selected from isocyanic ester, formamyl hexanolactam, formaldehyde, epoxide, halogen, protonic acid, acid anhydrides, carboxylic acid halides, oxychloride, trimetaphosphate or alkoxysilane-functional group and their combination.

It advantageously can be to be selected from following compound:

Diisocyanates and polyisocyanates; Preferably 4; 4 '-dicyclohexyl methane diisocyanate (H12MDI), methylene radical biphenyl diisocyanate (MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), two isocyanic acids, six methylene esters (HMDI) and LDI (LDI)

Diamino-formyl radical hexanolactam class, preferred 1, the two hexanolactams of 1 '-carbonyl,

The starch of oxalic dialdehyde, DAS and TEMPO-oxidation,

The di-epoxide class,

Halohydrin promptly comprises the compound of a kind of epoxide functional group and a kind of halogen functional group, Epicholorohydrin preferably,

The organic diacid class, preferred Succinic Acid, hexanodioic acid, pentanedioic acid, oxalic acid, propanedioic acid or toxilic acid, and corresponding acid anhydrides,

The oxychloride class, preferred phosphorus oxychloride,

Three metaphosphoric ester classes, preferred Trisodium trimetaphosphate,

The alkoxyl silicone alkanes, preferred tetraethoxysilane, and

And the mixture of these compounds.

In a preferred embodiment of the invention, this coupling agent is a kind of vulcabond, methylene radical biphenyl diisocyanate (MDI) or 4 particularly, 4 '-dicyclohexyl methane diisocyanate (H12MDI).

With dry weight represent and with respect to the value of the coupling agent of the summation of the thing of representing with dry weight equally combined according to the invention advantageously by weight between 0.1% and 15%, preferably by weight between 0.1% and 12%, still more preferably by weight between 0.2% and 9% and particularly by weight between 0.5% and 5%.

But randomly preferably with this coupling agent mix according in the compsn of the present invention can through under cool condition or physical mixed at low temperatures but preferably carry out through the kneading of (under temperature) under heat condition greater than the second-order transition temperature of this starch composites.This kneading temperature is advantageously between 60 ° of C and 200 ° of C, still better between 100 ° of C and 180 ° of C.This mixing can be carried out through hot mechanically mixing in batches or continuously and particularly online.In this case, this mixing time can be to be as short as from several seconds to several minutes.

Can preferably include the reagent that improves its resistance to impact shock according to compsn of the present invention, specifically be under the temperature of 23 ° of C or under the lower temperature.It can be a kind of ethylene/propene copolymer type (specifically being ethylene/propene tripolymer (EPDM) type), ethylene/styrene copolymer analog like or styrene/butadiene copolymers type, tree elastomer, styrene/butadiene/styrene (SBS) or the elastomerics of styrene/ethylene/butylene/styrene (SEBS) copolymer type or any other elastomer material.This improvement reagent can be rendered as according to 1% to 15%, preferably from 2% to 12% and still better from 5% to 10% of compsn of the present invention.

Individually or in combination, the preferred alternate forms below this thermoplastic compounds (a) has advantageously represented:

This thermoplastic starch is from granular starch, obtain from water soluble starch or from organically-modified starch, preferably wheat or pea granular starch, water soluble starch or organically-modified starch,

This thermoplastic starch shows and is lower than 5%, preferably is lower than 1% crystallinity, that is to say the state that is in basic amorphous,

This polyolefine is to be selected from Vilaterm (PE) and Vestolen PP 7052 (PP), and preferably includes some polyolefine, and wherein at least a is functionalized, that is to say and carried functional group, and like silane, vinylformic acid or maleic anhydride unit,

This polyolefine is a kind of polymkeric substance; It with respect to the combined carbon that in said polymkeric substance, exists comprise at least 50%, preferred at least 70%, particularly greater than 80% and the carbon of 100% the renewable source in standard A STM D 6852 and/or standard A STM D 6866 implications better still

This thermoplastic compounds (a) comprises at least a softening agent; This softening agent is selected from the mixture of di-alcohols, ternary alcohols and polyalcohols such as glycerine, poly-glycerol, Isosorbide, sorbitanic, Sorbitol Powder, N.F,USP MANNITOL and hydrogenant glucose syrup, organic acid salt such as Sodium.alpha.-hydroxypropionate, urea and these products

This thermoplastic compounds (a) comprises the reagent of at least a its resistance to impact shock of improvement; This reagent specifically is selected from elastomerics or any other elastomer material of polymkeric substance, ethylene/styrene or styrene/butadiene copolymers class, tree elastomer, vinylbenzene/butylene/styrene (SBS) or styrene/ethylene/butylene/styrene (SEBS) copolymer analog of ethylene/propene

This thermoplastic compounds (a) comprises at least a coupling agent that is selected from the compound that has at least two identical or different and free or functional groups of sheltering; These functional groups are selected from: isocyanic ester, formamyl hexanolactam, aldehyde, epoxide, halogen, protonic acid, acid anhydrides, carboxylic acid halides, oxychloride, three metaphosphoric esters or alkoxysilane-functional group and their combination

This thermoplastic compounds (a) with respect to all carbon that in said compsn, exist comprise at least 30%, advantageously at least 51%, preferred at least 70%, particularly greater than the carbon of 80% the renewable source in standard A STM D 6852 and/or standard A STM D 6866 implications

This thermoplastic compounds is in standard EN 13432, and is non-biodegradable or can not compost in the implication of ASTM D 6400 and ASTM D 6868,

Perhaps the maximum flexural strength that also shows of this thermoplastic compounds is greater than 50MPa, is preferably greater than 100MPa.

Secondly, must comprise synthon (b) according to compsn of the present invention.To these fibers select in case show between 2 microns and 35 microns diameter and at 25GPa.m ³/ kg and 230GPa.m ³Specific modulus between the/kg, and still it is selected the stability of heat and the purpose of thermo-mechanical property, its transport properties and/or its organoleptic properties (like its outward appearance, its color or its smell) thereof in addition to start from the cold mechanical characteristics of improving according to compsn of the present invention.Can also advantageously select nucleogenesis or crystallizing power, and make it to regulate shrinkage character according to compsn of the present invention with increase existence in this thermoplastic compounds (a) to them.

They can be selected from spun glass, thomel, steel fiber and synthetic polymer fiber particularly; These fibers have according to dsc measurement greater than 180 ° of C and be preferably greater than the fusing point of 200 ° of C and/or have greater than 70 ° of C and be preferably greater than the HDT (heat-drawn wire of 100 ° of C; ISO 75; Method Bf; Under 0.45MPa); And more specifically can be selected from short glass fiber, long glass fibres, high-tenacity thomel, HM carbon fibre, low modulus aromatic polyurethane fiber, high modulus fibre, polyethyleneterephthalate (PET) fiber, polybutylene terephthalate (PBT) fiber, Vestolen PP 7052 (PP) fiber, PS (PS) fiber, tynex (specifically is PA 6, PA 4; 6, PA 6,6 or aromatic series PA), urethane (PU, TPU) fiber or PLA fiber (specifically being the PLLA/PDLA stereocomplex).

Advantageously comprise by weight between 10% and 60%, according to compsn of the present invention (when it is intended to be used for be shaped according to a kind of common process that uses at plastics technology) for example by weight 10% and 40% or even synthon between 15% and 30% (b) by weight.These synthon (b) amount by weight can be advantageously between 20% and 50%, in fact even between 25% and 45%.So; Preferably showed lower melt flow according to compsn of the present invention; That is to say; According to ISO 1133 methods, under 190 ° of C for the weight of 2.16kg, preferably at the MFR between 2g/10 minute and 50g/10 minute better between 1g/10 minute and 100g/10 minute and still.

On the other hand; When compsn according to the present invention is intended to be shaped according to the routine techniques that in textile industry, uses, it advantageously comprises by weight from 40% to 90%, preferred by weight from 60% to 90%, and more preferably from 70% to 90% synthon (b) by weight.Under this situation, thermoplastic compounds (a) is advantageously used for sticker, tackiness agent, cementing agent, soaker, insulating covering agent or the Hydrogenated Polyisobutene of synthon (b).So; It has preferably embodied a high melt flow, that is to say, according to ISO 1133 methods; Under 190 ° of C for the weight of 2.16kg, preferably between 25g/10 minute and 500g/10 minute and still better 100 and 500g/10 minute between MFR.

The diameter that these synthon (b) are advantageously showed is between 2 microns and 35 microns, preferably between 5 microns and 30 microns and still better between 8 microns and 15 microns.When considering spun glass, the diameter of independent fiber is normally between 3 microns and 30 microns, be between 10 microns and 14 microns more routinely.As for short glass fiber (their length generally is on 3 millimeters to 4 millimeters magnitude when introducing), in compsn according to the present invention their length normally at 200 microns near 300 microns.For " length " fiber, in compsn according to the present invention, their length can reach from several millimeters to tens of centimetres.These synthon (b) preferably show in addition between 60GPa and the 450GPa and more favourable the highest tensile modulus between 70GPa and 400GPa.

In addition, can comprise other polymkeric substance of a spot of any character, so that regulate its characteristic according to compsn of the present invention.Yet; It will preferably include the partially or completely polymkeric substance or the multipolymer of biogenetic derivation; Particularly like urethane (PU), thermoplastic polyurethane (TPU), polymeric amide or polyester, specifically be following type: polybutylene terephthalate class (PBT), polyethyleneterephthalate class (PET), aliphatic copolyester-altogether-terephthalate class (PBAT), polylactic acid-based (PLA), gather succsinic acid fourth diester class (PBS, PBSA) or gather hydroxyalkyl alkanoic acid ester class (PHA, PHB, PHBV).

Other additives of weighting agent and any character (comprise following detailed description those) can be integrated with according in the compsn of the present invention.

They can be that target is further to improve its physics-chem characteristic (particularly its physical structure), its processing behavior and weather resistance thereof, or the product of the characteristic of in addition its machinery, heat, conduction, adherent or sense organ.

This additive can be the reagent that improves or regulate machinery or thermal property, and it is selected from inorganic materials, salt and organic substance.It can relate to nucleator, for example talcum, relate to increase-volume or dispersion agent, for example natural or synthetic tensio-active agent, relate to the reagent that improves shock strength or scrath resistance; For example Calucium Silicate powder, relate to the inotropic reagent of adjustment, Magnesium Silicate q-agent for example relates to the reagent of catching water, acid, catalyzer, oxygen, ir radiation or UV radiation or making its inactivation; Relate to hydrophobizing agent; For example oils and lipid relate to fire retardant and fireproofing agent, for example halogenated verivate; Relate to smoke suppressant or relate to inorganic or organic reinforcing filler, for example lime carbonate or talcum.

This additive can also be a kind of reagent; It improves or regulates conduction or insulation characterisitic or stopping property (for example for air, water, gas, solvent, fatty substance, gasoline, spices or fragrance) for electricity or heat; Specifically be to be selected from inorganic materials, salt and organic substance; Particularly be selected from the reagent of conduction or dissipation heat, for example metal-powder and graphite.This coolant can also be to be selected from ceramic-like.

This additive can also be a kind of reagent that improves organoleptics property, specifically:

Odor property (perfumery or odor masking agent class),

Optical characteristics (gloss-imparting agent class, whitening agent class, like titanium oxide, dye class, pigment class, dye enhancer class, opalizer class, matting agent class (mattness agents) like lime carbonate, thermochromism agent class, phosphorescence and fluorescent agent class, metalating agent or marble grain agent (marbling agents) and antifogging agent class);

Sound property (permanent white and tiff); And

Tactile characteristics (fatty substance, silicone oil).

This additive can also be a kind of reagent that improves or regulate adhesion characteristics; The adhesion of material, textile material and the inorganic materials of particularly processing for cellulose materials such as paper or timber, metallic substance such as aluminium and steel, glass or pottery, it specifically is for example rosin, rosin, ethylene/vinyl alcohol copolymer, fatty amine, lubricant class, releasing agent class, static inhibitor class and anti-caking agent class.

At last; This additive can be improve material weather resistance a kind of reagent or control a kind of reagent of its (biology) degradability; Particularly be selected from: hydrophobizing agent class such as oils and fats, corrosion inhibitor class, biocide class such as Ag, Cu and Zn; Decomposition catalyst class such as oxo catalyst class, and enzyme such as amylases.

Preferably, this additive can be selected from aspect aging and carry out stable reagent, especially UV stablizer, hydrophobizing agent and biocide.

According to the purpose of compsn of the present invention, can use moment that several different methods comes to provide extremely different particularly and order to introduce the component of said compsn (polyolefine, starch, optional softening agent, synthon (b), optional coupling agent, optional being used to improve reagent, other optional additives of resistance to impact shock) from preparation.

Therefore, synthon can be after in advance it partly or entirely being dispersed in this thermoplastic compounds (a), to introduce.

In all these possibilities that are used for handling said component, particularly, a theme of the present invention is a kind of advantageous method that is used to prepare the compsn of as above describing with its all alternative forms, and said method comprised with the next stage:

(i) select at least a thermoplastic compounds (a), this thermoplastic compounds comprises at least a polyolefine and at least a thermoplastic starch,

(ii) select that at least one class has a diameter between 2 microns and 35 microns and have at 25GPa.m ³/ kg and 230GPa.m ³The synthon of the specific modulus the between/kg (b),

(iii) this thermoplastic compounds (a) is mixed, is preferably hot mechanically mixing with these synthon (b), so that obtain compsn based on vegetable material and synthon.

In thermoplastic compounds (a), combine these synthon (b) perhaps this thermoplastic compounds (a) to be applied in these synthon (b) and can and to carry out before their hot mechanically mixing under cool condition.This mixed ideal ground carries out under heat condition, that is to say under a temperature greater than the highest second-order transition temperature of this thermoplastic compounds (a).This temperature can be between 60 ° of C and 280 ° of C, for example between 60 ° of C and the 250 ° of C, or preferably between 80 ° of C and the 200 ° of C and particularly between 100 ° of C and 185 ° of C.From promoting fiber to be attached to the purpose in the thermoplastic compounds, this temperature can be quite high, for example between 200 ° of C and the 280 ° of C, preferably between 220 ° of C and 270 ° of C.This hot mechanically mixing can carry out in batches, for example through kneading/mixing, perhaps continuously, for example through extruding or coextrusion.According to selected blending means, the scope of this blended time length can be from several seconds to several hours.Preferably, the scope of mixing time be from several seconds to several minutes, for example from 10 to 75 seconds.

According to a preferred method of the present invention, (ii) select in the process spun glass as synthon in the stage, and stage mixing (iii) is through between 200 ° of C and the 280 ° of C, preferably under the temperature between 220 ° of C and the 270 ° of C, extrude and carry out.In these TRs, successfully realized the very uniformly dispersion of spun glass (b) in this thermoplastic compounds (a).In fact, when this thermoplastic starch is extruded separately, observed the higher loss of the mechanical characteristics of this thermoplastic starch, and this loss is relevant with the thermolysis of starch and softening agent under greater than the temperature of 200 ° of C.If attempt spun glass is attached in this thermoplastic starch, this decomposition or even bigger, its reason is the increasing considerably of viscosity in cohesive process.Beat allly be that though the thermoplastic starch that this thermoplastic compounds (a) comprises not is very heat-staple, the method that is used to make said composition has no to carry out difficultly and the mechanical characteristics of the compsn that obtains by this method is outstanding.

Applicant company shows; With respect to the traditional method of producing based on the mixture of polyolefine and fiber; This method according to the present invention is being highly favourable aspect the energy, and its reason is to have selected specific thermoplastic compounds (a) and had thermoplastic starch therein.

Can comprise according to the method for the invention one follow-up or with (iii) simultaneously stage of mix stages, promptly between 60 ° of C and 280 ° of C, for example between 80 ° of C and 250 ° of C, preferably between 120 ° of C and the 200 ° of C and special this is based on a kind of shaping processing of the compsn of vegetable material and synthon (iv) under the temperature between 160 ° of C and the 185 ° of C.

In addition, another theme of the present invention is to use a kind of compsn that comprises at least a plastifying of part at least starch as the expanding material between synthon (b) and a kind of polyolefine.

Can former state use or a kind of mixture of conduct and other products or additive (polymkeric substance that comprises other synthetic or synthetical polymkeric substance or natural origin) uses according to thermoplastic compounds of the present invention.It is preferably not biodegradable and can not compost on the meaning of EN 13432, ASTM D 6400 and ASTM D 6868; And for this reason; Through its abundance bigger in the plant prod in photosynthetic source, it has constituted a kind of carbon trap or catcher.

According to the method that is used for quantitatively determined renewable source carbon of ASTM D 6866, totally representing with respect to said compsn, compsn according to the present invention advantageously comprises at least 25%, preferred at least 30% and particularly greater than 40% renewable source material.The carbon of this renewable source is the component carbon of the starch that in compsn according to the present invention, must exist but also can is the carbon of other selectable components of carbon, the said composition of polyolefine (preferably biogenetic derivation), if like softening agent, this softening agent is glycerine or Sorbitol Powder, or is derived from any other products of renewable natural resource particularly.

Specifically; Might imagine use compsn according to the present invention as biological plastics material or matrix material; Be used for through injection molding, extrude, blow molding, calendering, molded, hot compacting, compacting (compacting), spinning, " acupuncture " or other technologies prepare article, parts, bottle, jar, container, storage tank, sheet material, panel, pole stock, carriage, beam part, tables, indoor furniture, street furniture, felt, non-woven fabric, door lining, wall, insulation layer, trolley part, electric component, cable, epitheca, instrument panel, cover cap or other civilian standard prods; Like sporting equipment and amusement article, civil electric appliance, the instrument that in different industry, uses, for example as building, packing, electric power, transportation, aviation, boats and ships and equipment industry.

Said compsn can provide with the form of powdered, granulous or bead.It can in statu quo constitute is intended to await the masterbatch that dilutes in the matrix in a kind of biogenetic derivation or abiotic source or the matrix of masterbatch.It can also constitute a kind of plastics parent material or a kind of compound, and this parent material or compound can directly be used by the moulding press of the routine of a kind of component manufacturer or plastic article.It can also form a kind of final or intermediary compsn, and said composition can be shaped or be used for textile industry as fiber mat or non-woven or in wood-processing industry, be used as plank or wooden/polymer complex.

To obtain better understanding of the present invention by following instance, these instances under any circumstance all are not intended to limit the present invention.

Embodiment:According to the present invention with according to the multiple compsn of prior art

These preparation of compositions

What be elected to be thermoplastic compounds (a) for present embodiment is a kind of compsn based on and the following:

52%, that be called " AP6040 " by weight compsn, as described in the above-mentioned patented claim WO 2009/095617, WO 2009/095618 and the WO 2009/095622 that submit to by applicant company,

A kind of polyolefine of 46% by weight, this polyolefine comprise half the commercial polypropylene and second half the Vestolen PP 7052 with maleic anhydride graft, and

About 2% hexichol methylene vulcabond (MDI).

This compsn comprises the renewable source material of 52% the form that is in wheat starch, and the polyalcohols softening agent of biogenetic derivation.Under 190 ° of C, for the weight of 10kg, it shows about 1.11 density and 26g/10 minute MFR.This thermoplastic compounds (a) is called as: Resin A.

(test 1) prepares as synthon (b) as thermoplastic compounds (a) and spun glass through only using Resin A according to a kind of compsn of the present invention, and it shows:

About 30GPa.m ³The specific modulus of/kg,

About 1GPa.m ³The specific stress of/kg,

2.2GPa high tensile,

The highest tensile modulus of 75GPa,

4.8% elongation at break,

And the diameter of 10 microns individual fibers.

The spun glass of the trade weight with about 40% mixes with this thermoplastic compounds Resin A.

It is following to extrude the condition for preparing through the 6mm die orifice:

Temperature profile from 240 ° of C to 260 ° of C;

Macrofiber is handled special-purpose dipping die orifice;

The amount of passing through of 200kg/h.

At the outlet of extruder place, these rods cool off and are cut to then the length of 1cm under water.Thus obtained density according to compsn of the present invention is about 1.25.

Through replacing Resin A with a kind of mixture; Using equally in an identical manner, about 40% content of glass fiber has prepared a reference composition that is called G400-8229; This mixture comprises a kind of 60g/10 of having minute MFR (230 ° of C of 97%; 2.16kg), Vestolen PP 7052 and a kind of MFR (230 ° of C of PPH60 homopolymer class with 450g/10 minute; 2.16kg), the polyacrylic mixture of PPH450 homopolymer class, and with 1% maleic anhydride (PPg) grafted 3% Vestolen PP 7052 as expanding material.Extrusion condition through the 6mm die orifice is only arranged by slight modification, its mode increases to 300 ° of C for this characteristic from 280 ° of C.

Also use with the 1 identical method of testing to have prepared according to a compsn of the present invention (test 2), said composition and reference composition G400-8229 are identical, except having substituted PPH60 with Resin A.

At last, with the comparing of test 2 identical conditions and PPH450, Resin A and PPg Prepared under the example according to a compsn of the present invention (test 3), except the amount of spun glass is By weight 30%.

Using Resin A to replace in the process of PPH mixture, industrial test does not show any special problem, except for test 1, and some thickness and cause the fracture of spun glass too of melt.

According to the present invention with according to the mechanical characteristics of these compsns of prior art:

Viewed situation is; Under the content of glass fiber that equates; Compsn according to the present invention shows extraordinary mechanical features and for measured index, is suitable (if not better words) according to the compsn of test 2 and according to prior art combinations.

Resin A it seems has influenced adhering improvement and the improvement on these fibers and polyacrylic consistency to spun glass.

In addition, can obtain through the same procedure of normal use, and advantageously need not change equipment and work under the lesser temps of 20 ° of C to 35 ° of C under the reference composition simultaneously according to compsn of the present invention.This advantageously feasible conserve energy significantly, and make it to reduce the requirement to the resource of fossil sources.

In addition, shown natural outward appearance according to compsn of the present invention (different) with prior art.It has also shown comfortable sensation, and this can obtain explaining through the existence of starch in this thermoplastic compounds (a) and the synthetic elastomer that therefore uses for this purpose, be dispersed in wherein.

Have been found that; Comprise about altogether 31% biogenetic derivation material, according to test 1 compsn of the present invention; Comprise about altogether 16% biogenetic derivation material, according to test 2 compsns of the present invention; Comprise about altogether 18% biogenetic derivation material, according to test 3 compsns of the present invention, with do not contain any renewable natural origin material, compare according to the reference composition of prior art, the three has represented the advantage in many industry.

As explained above, the reinforce that adds from the deflection that improves a kind of compsn and stretched mechanical characteristic purpose is attended by the reduction on the resistance to impact shock usually.For example, applicant company has been found that the deflection of this compsn and stretched mechanical characteristic are modified when in based on thermoplastic starch and polyolefinic a kind of compsn, adding clay or lime carbonate, but also observes the reduction on the resistance to impact shock.

In the time will comparing with the characteristic that compsn obtained that does not have spun glass (Resin A) for compsn according to the present invention; Applicant company is found thus; Through adding specific synthon based on thermoplastic starch and polyolefinic compsn to a kind of; This might improve the deflection and the stretched mechanical characteristic of this compsn, and has unexpectedly increased these resistance to impact shocks based on the compsn of polyolefine and thermoplastic starch simultaneously.

Claims (25)

1. compsn based on vegetable material and synthon is characterized in that said composition comprises:

A kind of thermoplastic compounds (a) of at least 10% and maximum by weight 95% by weight, this thermoplastic compounds comprises at least a polyolefine and at least a thermoplastic starch, and

At least 5% and maximum by weight 90% synthon (b) by weight, these fibers have the diameter between 2 microns and 35 microns and have at 25GPa.m ³/ kg and 230GPa.m ³Specific modulus between the/kg.

2. compsn as claimed in claim 1; It is characterized in that, said composition be with can be through compacting, hot compacting, extrude, the form of particle, chip, sheet material, sheet material, powder or fiber mat that calendering, spinning, injection molding or air blowing form provides.

3. according to claim 1 or claim 2 compsn is characterized in that, this thermoplastic compounds (a) has according to ISO 1183 methods between 1.1 and 2.5, preferably between 1.15 and the 2.10 and more preferably density between 1.3 and 2.0.

4. any one described compsn as in the above claim is characterized in that, said composition have according to ISO 178 methods greater than 1500MPa, be preferably greater than 3000MPa and still better greater than the modulus in flexure of 5000MPa.

5. like any one described compsn in the above claim; It is characterized in that; This thermoplastic compounds (a) comprises polyolefine at least a virgin material or that utilize again; This polyolefine is selected from high density polyethylene(HDPE) class (HDPE), new LDPE (film grade) class (LDPE), straight-chain low density polyethylene class, HPP homopolymer polypropylene class (PPH), Atactic Polypropelene class (RPP), polypropylene copolymer class (PPc) and polybutylenes class, and also has their any blend.

6. any one described compsn as in the above claim is characterized in that, this thermoplastic compounds (a) comprise at least a from the monomer of biogenetic derivation, specifically be the polyolefine that obtains from bio-ethanol or biological methanol.

7. any one described compsn as in the above claim is characterized in that this thermoplastic compounds (a) comprises thermoplastic starch, and the percent crystallinity of this thermoplastic starch is less than 15%, preferably less than 5% and be more preferably less than 1%.

8. like any one described compsn in the above claim; It is characterized in that; This thermoplastic compounds (a) comprises at least a thermoplastic starch, and this thermoplastic starch accounts for more than 25% of this thermoplastic compounds (a), preferred more than 35% and more preferably more than 50% by dry weight basis.

9. like any one described compsn in the above claim; It is characterized in that this thermoplastic compounds (a) comprises that at least a plastifying starch that obtains from and the following is as thermoplastic starch: any mixture of fatty ester, dextrin, maltodextrin and these products of the aliphatic chain of the fatty ester of the starch of native starch, pregelatinized starch, extrusioning starch, atomizing starch, fluidization starch, Sumstar 190, cationic starch, anionic starch, hydroxyalkylation, cross-linking starch, starch acetate, starch and 4 to 22 carbon.

10. like any one described compsn in the above claim, it is characterized in that this thermoplastic compounds (a) comprises at least a softening agent; This softening agent preferentially is selected from glycols, ternary alcohols, polyalcohols; The hydrogenant glucose syrup, organic acid salt, urea; The ester class of organic acid methyl, ethyl or fat, the acetate of single alcohol, glycol, trivalent alcohol or polyvalent alcohol or the ester class of fat, and any mixture of these products.

11. as any one described compsn in the above claim; It is characterized in that, the plasticizer loading in this thermoplastic compounds (a) by dry weight basis be this thermoplastic compounds (a) 4% and 50% between, preferably between 8% and 40% and especially between 15% and 25%.

12., it is characterized in that in this thermoplastic compounds (a), this polyolefine is formed continuous disperse phase, and this thermoplastic starch is formed discontinuous disperse phase like any one described compsn in the above claim.

13., it is characterized in that this thermoplastic compounds (a) comprising like any one described compsn in the above claim:

From 25% to 85% thermoplastic starch by weight,

From 10% to 60% polyolefine by weight,

And from 4% to 40% at least a softening agent by weight, preferably be not water.

14., it is characterized in that this thermoplastic compounds (a) comprising like any one described compsn in the above claim:

From 35% to 80% thermoplastic starch by weight,

From 10% to 50% polyolefine by weight,

And from 10% to 30% at least a softening agent by weight, preferably be not water.

15. as any one described compsn in the above claim; It is characterized in that; These synthon (b) are to be selected from spun glass, thomel, steel fiber and synthetic polymeric fibers; These fibers have according to dsc measurement greater than 180 ° of C and be preferably greater than the fusing point of 200 ° of C and/or have greater than 70 ° of C and be preferably greater than the HDT temperature of 100 ° of C, and more specifically can be to be selected from short glass fiber, long glass fibres, high-tenacity thomel, HM carbon fibre, low modulus aromatic polyurethane fiber, high modulus fibre, polyethyleneterephthalate (PET) fiber, polybutylene terephthalate (PBT) fiber, Vestolen PP 7052 (PP) fiber, PS (PS) fiber, tynex, polyurethane fiber or PLA fiber (specifically being the PLLA/PDLA stereocomplex).

16. as any one described compsn in the above claim, it is characterized in that said composition comprises by weight from 10% to 60%, preferred by weight from 20% to 50% and still be more preferably from 25% to 45% synthon (b) by weight.

17., it is characterized in that the diameter of these synthon (b) is between 2 microns and 35 microns, preferably between 5 microns and 30 microns and still better between 8 microns and 15 microns like any one described compsn in the above claim.

18., it is characterized in that the tension fracture modulus of these synthon (b) is between 60GPa and the 450GPa and preferably between 70GPa and 400GPa like any one described compsn in the above claim.

19. as any one described compsn in the above claim; It is characterized in that; Said composition also comprises a kind of coupling agent; This coupling agent is to be selected from the compound that has at least two identical or different and free or functional groups of sheltering, and these functional groups are selected from isocyanic ester, formamyl hexanolactam, epoxide, aldehyde, halogen, protonic acid, acid anhydrides, carboxylic acid halides, oxychloride, three metaphosphoric esters or alkoxysilane-functional group and their mixture.

20., it is characterized in that said composition also comprises aging stabilizer, specifically be anti UV agent, hydrophobizing agent and biocide like any one described compsn in the above claim.

21. as any one described compsn in the above claim, it is characterized in that said composition is non-biodegradable or can not compost in the implication of standard EN 13432, ASTM D 6400 and ASTM D 6868.

22. as any one described compsn in the above claim; It is characterized in that; Said composition comprises at least 25%, preferred at least 30% and especially greater than 40% renewable source material, totally to represent with respect to said compsn according to the method that is used for quantitatively determined renewable source carbon of ASTM D 6866.

23. one kind is used for preparing like any one described method for compositions based on vegetable material and synthon of above claim, it is characterized in that it comprised with the next stage:

(i) select at least a thermoplastic compounds (a) that comprises at least a polyolefine and at least a thermoplastic starch,

(ii) select at least one type of diameter between 2 microns and 35 microns and specific modulus at 25GPa.m ³/ kg and 230GPa.m ³Synthon between the/kg (b),

(iii) this thermoplastic compounds (a) is mixed with these synthon (b), preferably carries out hot mechanically mixing, so that obtain this compsn based on vegetable material and synthon.

24. method as claimed in claim 23; It is characterized in that, this mix stages after (iii) be between 60 ° of C and 280 ° of C, for example between 80 ° of C and 250 ° of C, preferably between 120 ° of C and the 200 ° of C and under the temperature between 160 ° of C and the 185 ° of C, this compsn based on vegetable material and synthon is carried out a kind of shaping processing (iv) especially.

25. like claim 23 or 24 described methods; It is characterized in that comprising spun glass, and it is characterized in that this mix stages (iii) is between 200 ° of C and the 280 ° of C, preferably under the temperature between 220 ° of C and the 270 ° of C, carry out through extruding at these synthon that the stage is selected in (ii).