CN107936501A - Injection-molded item and preparation method thereof - Google Patents

Injection-molded item and preparation method thereof Download PDF

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Publication number
CN107936501A
CN107936501A CN201610892111.7A CN201610892111A CN107936501A CN 107936501 A CN107936501 A CN 107936501A CN 201610892111 A CN201610892111 A CN 201610892111A CN 107936501 A CN107936501 A CN 107936501A
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poly
acids
acid
cellulose
injection
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CN107936501B (en
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詹姆斯·洪学·王
周炳
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The present invention relates to a kind of thermoplastic cellulose, Microbe synthesis polyester, reactive monomer blend injection-molded item, it is high mainly to solve thermoplastic cellulose low temperature process process medium viscosity in the prior art, injection molding processability is poor, the technical problem for being limited its application field.The present invention is by using injection-molded item, and thermoplastic cellulose and Microbe synthesis polyester blend containing graft modification, in terms of mass fraction, thermoplastic cellulose and the Microbe synthesis polyester blend of the graft modification include following components：1) 20 to 80 parts of thermoplastic cellulose；2) 80 to 20 parts of Microbe synthesis polyester；3) 0.1 to 10 part of reactive monomer；It is characterized in that reactive monomer is at least grafted to thermoplastic cellulose and the technical solution on Microbe synthesis polyester one in the blend, preferably solves the problems, such as this, in the industrial production available for biodegradable injection-molded item.

Description

Injection-molded item and preparation method thereof
Technical field
The invention belongs to injection-molded item field, has body Wataru and a kind of thermoplasticity of the graft modification with the special rheological equationm of state The blend injection-molded item of cellulose and Microbe synthesis polyester, this invention is and Wataru and a kind of prepare with the special rheological equationm of state The thermoplastic cellulose of graft modification and the method for Microbe synthesis polyester blend injection-molded item.
Technical background
Cellulose is the organic polymer that reserves are most on the earth, and the most biological material of annual reproducible amounts. Cellulose is the structural material in non-green plant cell wall, and xylophyta contains the cellulose of about 30-40%, cotton fiber then contains There is about 90% cellulose.The major commercial use of cellulose is paper and cardboard, separately has a small amount of cellulose to be used to prepare such as match The regenerated celluloses such as fine jade phenol (Cellophane), viscose glue (Rayon) and some fibre element derivative.
Since cellulose is the natural polymer that plant changes into the carbon dioxide in air and water by photosynthesis, Therefore the carbon in cellulose belong to fixed in the recent period carbon and different from fossil fuel and its petroleum chemicals such as oil or coals In millions of years before fixed carbon, the carbon that different times are fixed can pass through14C isotope standardizations are examined Survey.Due to these difference, had based on bio-based high molecular products prepared by biomass material relative to petroleum base high molecular products There is the advantage of raw material low-carbon, then using low energy consumption and the production technology of low-carbon emission, it is possible to produce the high score of green low-carbon Sub- product.For such consideration, natural polymer, including cellulose, hemicellulose, lignin, starch, chitin etc., and its Derivative Tetramune receives increasingly increased concern and research and development in the whole world, to develop good green low-carbon environment-friendly product.And The extensive use of the green low-carbon product of (Life Cycle Assessment) confirmation is assessed by Life Cycles, it will help Green production and Green Lifestyle are supported, to reduce the content of the greenhouse gases (carbon dioxide etc.) in air and alleviation The climate change in the whole world contributes.
Although cellulose has the advantages that the low-carbon on raw material, the cellulose amount as plastic injection product application is seldom, This is because the heat decomposition temperature of cellulose is less than its fusing point without thermoplastic properties.To overcome this defect of cellulose, Researcher have developed the regenerated cellulose of solwution method production, i.e., cellulose or cellulose derivative is first dissolved in solvent In, by solution machine-shaping, it is changed into cellulose again after being prepared into film or spinning, the viscose rayon in textile industry is adopted Prepare in this way.
In addition for cellulose derivative when three hydroxyls on each of which repetition dehydrated glucose unit are through enough changes After learning transformation, can also have relatively low fusing or plasticization temperature, limited thermoplastic processing can be carried out, become thermoplastic fibre Element, this kind of material include the cellulose esters and cellulose ether of certain substitution value.Yield and production due to this kind of cellulose derivative Kind class is limited, and the viscosity of industrialized such product is higher, is especially apparent under compared with low processing temperature, is not suitable for needing The processing method of low melt viscosity such as spinning, injection etc.；Cellulose esters and cellulose ether, which have, at present is greatly used as coating Or the additive of adhesive field【High Zhenhua, Di Mingwei,《Biological material and application》, 2008】.Therefore, from processed and applied Angle, has exploitation low viscosity and the technical need of the thermoplastic cellulose derivative with excellent machinability, to meet correlation The market demand of raw material.
So far, there has been no the thermoplastic cellulose and Microbe synthesis polyester blend of reported in literature graft modification Special rheological behaviour, and in the prior art thermoplastic cellulose and Microbe synthesis polyester blend are effectively reduced without offer Melt viscosity method, be restricted the application of this kind of blend.
Thermoplastic cellulose and Microbe synthesis polyester blend melt viscosity are effectively reduced the invention discloses a kind of Continuous fusion extrusion method, it was found that unexpected phenomenon with as a result, disclosing the blend group with the special rheological equationm of state Into, and the blend has successfully been applied to injection-molded item field.
The content of the invention
Present invention solves the technical problem that one of be thermoplastic cellulose and Microbe synthesis polyester blend in the prior art Thing melt viscosity is excessive and the problem of may not apply to need injection-molded item prepared by low melt viscosity, there is provided it is special that one kind has The thermoplastic cellulose of the graft modification of the rheological equationm of state and Microbe synthesis polyester blend injection-molded item, the injection-molded item use Blend material effectively the viscosity " unexpected " of blend can be fallen below thermoplastic fibres element and microorganism is closed Into the blending addition theoretical viscosity of polyester starting material；So that there is the blend realization at a lower temperature injection-molded item is made Processing performance, better than the similar blend of the prior art, and since blend melt viscosity is low, it can be made in process It is more energy saving.
The second technical problem to be solved by the present invention, which is to provide, a kind of prepares the graft modification with the special rheological equationm of state Thermoplastic cellulose and Microbe synthesis polyester blend injection-molded item method, the melt for the blend that this method obtains glues Degree is in low shear rate (100s-1) under the conditions of it is at least lower by about 50% than the blending addition theoretical value of two kinds of starting materials；Cut in height Cutting speed rate (1363s-1) under the conditions of it is at least lower by 45% than the blending addition theoretical value of two kinds of starting materials.
One of in order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：A kind of injection-molded item, containing grafting Modified thermoplastic cellulose and Microbe synthesis polyester blend, in terms of mass fraction, the thermoplastic fibre of the graft modification Element includes following components with Microbe synthesis polyester blend：
(1) 20 to 80 part of thermoplastic cellulose；
(2) 80 to 20 parts of Microbe synthesis polyester；
(3) 0.1 to 10 parts of reactive monomer；
Wherein, reactive monomer is at least grafted to thermoplastic cellulose and Microbe synthesis polyester one in the blend On.
In above-mentioned technical proposal, the injection-molded item by the graft modification thermoplastic cellulose and Microbe synthesis Polyester blend is prepared, wherein the thermoplastic cellulose of the graft modification has with Microbe synthesis polyester blend The special rheological equationm of state, such as but the melt viscosity of the preferably blend is not limited in low shear rate 100s-1Under the conditions of two kinds of ratio The blending addition theoretical value at least low 50% of predominant starting material；In high-rate of shear 1363s-1Under the conditions of starting main than two kinds The blending addition theoretical value raw material at least low 45% of raw material.
In above-mentioned technical proposal, " two kinds of predominant starting materials " refers to that thermoplastic cellulose and Microbe synthesis gather Ester
In above-mentioned technical proposal, the substitution value of the thermoplastic cellulose is preferably greater than 1.0；The cellulose being more suitable for spreads out The substitution value of biology is more than 1.5, and the substitution value of particularly suitable cellulose derivative is more than 2.0.
In above-mentioned technical proposal, the thermoplastic cellulose is preferably cellulose acetate-butyrate, acetic acid valeric acid fiber Plain ester, acetic acid cellulose caproate ester, acetic acid enanthic acid cellulose esters, laurate cellulose esters, acetic acid cellulose pelargonate ester, acetic acid Capric acid cellulose esters, acetic acid laurate cellulose esters, acetic acid palmitic acid cellulose esters, acetic acid cellulose stearate ester, propionic acid fourth Acid cellulose ester, propionic acid cellulose valerate ester, propionic acid cellulose caproate ester, propionic acid enanthic acid cellulose esters, propionic acid octanoic acid cellulose Ester, propionic acid cellulose pelargonate ester, propionic acid capric acid cellulose esters, propionic acid laurate cellulose esters, propionic acid palmitic acid cellulose esters, third Sour cellulose stearate ester etc..
In above-mentioned technical proposal, the Microbe synthesis polyester be by microbial fermentation processes prepare both can be complete Biodegradable and bio-based completely polyester.
In above-mentioned technical proposal, the Microbe synthesis polyester is preferably：Poly 3-hydroxy butyrate (PHB), poly- 3- hydroxyls Base valerate (PHV), poly- 3- hydroxycaproic esters (PHH), poly- 3- hydroxyheptanoates, poly- 3- Hydroxyoctanoic acids ester, poly- 3- hydroxynonanoic acids Ester, poly- 3- hydroxydecanoic acids ester, poly- 3- hydroxydecanoic acids ester, poly- 3- hydroxylaurics acid esters, poly- 3- hydroxyls palmitate, poly- 3- hydroxyls are hard The equal polyester of the Microbe synthesis such as resin acid ester and poly- 3-hydroxybutyrate -3- hydroxyl valerates (PHBV, P3HB3HV), poly- 3- hydroxyls - 4 butyric ester of base butyric acid (P3HB4HB), poly- 3-hydroxybutyrate -3- hydroxycaproic esters (PHBHx or 3HBHx), poly- 3- hydroxyls Butyric acid -3- hydroxyheptanoates, poly- 3-hydroxybutyrate -3- Hydroxyoctanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxynonanoates, poly- 3- hydroxyls Base butyric acid -3- hydroxydecanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxylauric acid esters, poly- 3-hydroxybutyrate -3- hydroxyl palmitates, Poly- 3-hydroxybutyrate -3- hydroxy stearic acid esters；Poly- 3- hydroxypentanoic acids -3- hydroxycaproic esters, poly- 3- hydroxypentanoic acids -3- hydroxyheptanoic acids Ester, poly- 3- hydroxypentanoic acids -3- Hydroxyoctanoic acid esters, poly- 3- hydroxypentanoic acids -3- hydroxynonanoates, the poly- 3- hydroxypentanoic acids -3- hydroxyl last of the ten Heavenly stems Acid esters, poly- 3- hydroxypentanoic acids -3- hydroxylauric acid esters, poly- 3- hydroxypentanoic acids -3- hydroxyl palmitates, poly- 3- hydroxypentanoic acids -3- Hydroxy stearic acid ester；Poly- 3- hydroxycaproic acids -3- hydroxyheptanoates, poly- 3- hydroxycaproic acids -3- Hydroxyoctanoic acid esters, poly- 3- hydroxyls oneself Acid -3- hydroxynonanoates, poly- 3- hydroxycaproic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxycaproic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxyls Caproic acid -3- hydroxylauric acid esters, poly- 3- hydroxycaproic acids -3- hydroxyl palmitates, poly- 3- hydroxycaproic acids -3- hydroxy stearic acid esters； Poly- 3- hydroxyheptanoic acids -3- Hydroxyoctanoic acid esters, poly- 3- hydroxyheptanoic acids -3- hydroxynonanoates, poly- 3- hydroxyheptanoic acids -3- hydroxydecanoic acids Ester, poly- 3- hydroxyheptanoic acids -3- hydroxylauric acid esters, poly- 3- hydroxyheptanoic acids -3- hydroxyl palmitates, 3- hydroxyheptanoic acid -3- hydroxyls Stearate；Poly- 3- Hydroxyoctanoic acids -3- hydroxynonanoates, poly- 3- Hydroxyoctanoic acids -3- hydroxydecanoic acid esters, poly- 3- Hydroxyoctanoic acids -3- Hydroxydecanoic acid ester, poly- 3- Hydroxyoctanoic acids -3- hydroxylauric acid esters, poly- 3- Hydroxyoctanoic acids -3- hydroxyl palmitates, poly- 3- hydroxyls are pungent Acid -3- hydroxy stearic acid esters；Poly- 3- hydroxynonanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxynonanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxyls Base n-nonanoic acid -3- hydroxylauric acid esters, poly- 3- hydroxynonanoic acids -3- hydroxyl palmitates, poly- 3- hydroxynonanoic acids -3- hydroxy stearic acids Ester；Poly- 3- hydroxydecanoic acids -3- hydroxylauric acid esters, poly- 3- hydroxydecanoic acids -3- hydroxyl palmitates, poly- 3- hydroxydecanoic acids -3- hydroxyls At least one of copolyesters of Microbe synthesis such as base stearate.
In above-mentioned technical proposal, the Microbe synthesis polyester is more preferably：Poly 3-hydroxy butyrate, poly- 3- hydroxyls fourth Acid -3- hydroxyl valerates, the poly- butyric ester of 3-hydroxybutyrate -4, poly- 3-hydroxybutyrate -3- hydroxycaproic esters, poly- 3- hydroxyls fourth Acid -3- Hydroxyoctanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxynonanoates, poly- 3-hydroxybutyrate -3- hydroxydecanoic acid esters, poly- 3- hydroxyls Butyric acid -3- hydroxylauric acid esters, poly- 3-hydroxybutyrate -3- hydroxyl palmitates, poly- 3-hydroxybutyrate -3- hydroxy stearic acid esters etc. At least one of.
In above-mentioned technical proposal, the blending addition theoretical value of the melt index of the blend than two kinds of predominant starting materials It is at least high by about 90%.
In above-mentioned technical proposal, the reactive monomer is with hydroxyl, carboxyl, carbonyl, ester group, amino, sulfydryl, sulphur Acidic group, ehter bond, halogen, peptide bond, anhydride bond isopolarity group, and at least one in the compound also containing unsaturated carbon-carbon double bond Kind.The reactive monomer can react with other components in blend under certain condition, and then be grafted with covalent bond Onto other components, special modified effect is played.
In above-mentioned technical proposal, the reactive monomer is preferably maleic acid anhydride, acrylic compounds, methacrylic acid At least one of compounds such as class, esters of acrylic acid, methyl acrylic ester, acrylic amide, methacryl amine.
In above-mentioned technical proposal, the blend preferably further includes：The initiator of 0.01 to 1 mass parts.
In above-mentioned technical proposal, the initiator is radical initiator, is produced from for decomposable asymmetric choice net under certain condition By the organic compound of base, include but is not limited to：Acyl peroxide, such as benzoyl peroxide (BPO)；Alkyl (dialkyl group) Peroxide, such as dual-tert-butyl peroxide, double cumyl peroxides, cumyl peroxy butyl, 3,3,5- front threes Butylcyclohexane -1,1- diperoxies the tert-butyl group, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes etc.；Perester, such as crosses trimethyl Tert-butyl acetate, mistake -2 ethyl hexanoic acid tert-butyl ester, t-butyl perbenzoate, peroxidating lauric acid etc.；Alkyl peroxide, Such as tert-butyl hydroperoxide, isopropyl benzene hydroperoxide；Ketone peroxide, such as methyl ethyl ketone peroxide；Azo compound, such as azo Two isobutyl cyanogen (AIBN) etc..
In above-mentioned technical proposal, the initiator is preferably benzoyl peroxide, and azo-bis-isobutyl cyanide, peroxidating two are different Propyl benzene, di-t-butyl peroxide, tert-butyl hydroperoxide, perbenzoic acid, 2,5- dimethyl -2,5- di-t-butyls peroxide oneself At least one of alkane etc..
In above-mentioned technical proposal, the thermoplastic cellulose is preferably cellulose acetate-butyrate, Microbe synthesis polyester Preferably poly 3-hydroxy butyrate, poly- 3-hydroxybutyrate -3- hydroxyl valerates, poly- 3-hydroxybutyrate -3- hydroxycaproic esters etc., instead Answering property monomer is preferably hydroxyethyl methacrylate, glycidyl methacrylate etc., and initiator is preferably benzoyl peroxide first (double two or five) etc., have well between component of mixture at this time for acyl, 2,5- dimethyl -2,5- di-t-butyl hexane peroxide Compatibility, and mixture shows the special rheological equationm of state, can widen the use scope of starting material significantly, and meanwhile it is relatively low Melt viscosity can reduce energy consumption in material processing.
In above-mentioned technical proposal, the blend material is most preferably that the blend material contains 20 to 80 mass parts Thermoplastic cellulose, the Microbe synthesis polyester of 80 to 20 mass parts, the reactive monomer and 0.01 to 1 of 0.1 to 10 mass parts The initiator of mass parts, the synergistic function between component is most obvious at this time, obtained blend rheological property and compatibility It is optimal.
In above-mentioned technical proposal, the blend material further preferably contains compatibility agent, inorganic filler, antioxidant, lubrication At least one of agent, colouring agent etc..
In above-mentioned technical proposal, the melt viscosity of the blend injection-molded item is preferably in low shear rate (100s-1) Under the conditions of at least lower 65% than the blending addition theoretical value of two kinds of predominant starting materials (microorganism of preferably 50 to 20 mass parts is closed Into polyester and the thermoplastic cellulose of 50 to 80 mass parts, reactive monomer is 2 to 8 mass parts, and initiator is 0.05 to 0.2 matter Measure part), further preferably at least low 70% (the Microbe synthesis polyester of more preferably 35 mass parts and the thermoplasticity fibre of 65 mass parts Dimension element, reactive monomer is 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts).
In above-mentioned technical proposal, the melt viscosity of the blend injection-molded item is preferably in high-rate of shear (1363s-1) Under the conditions of at least lower 60% than the blending addition theoretical value of two kinds of predominant starting materials (microorganism of preferably 50 to 20 mass parts is closed Into polyester and the thermoplastic cellulose of 50 to 80 mass parts, reactive monomer is 2 to 8 mass parts, and initiator is 0.05 to 0.2 matter Measure part), further preferably at least low 65% (the Microbe synthesis polyester of more preferably 35 mass parts and the thermoplasticity fibre of 65 mass parts Dimension element, reactive monomer is 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts).
In above-mentioned technical proposal, the melt index of the blend injection-molded item is preferably than two kinds of predominant starting materials It is at least high by about 90% that addition theoretical value is blended, more preferably at least high about 200% (the preferably microorganism of 50 to 20 mass parts The thermoplastic cellulose of synthesizing polyester and 50 to 80 mass parts, reactive monomer are 2 to 8 mass parts, and initiator is 0.05 to 0.2 Mass parts), it is more preferably at least high by about 300% (the Microbe synthesis polyester of more preferably 35 mass parts and the thermoplastic of 65 mass parts Property cellulose, reactive monomer is 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts).
In above-mentioned technical proposal, the Microbe synthesis polyester (polyhydroxyalkanoate) includes the poly- hydroxyl fat of short-side chain Fat acid esters and middle side chain polyhydroxyalkanoate.Short-side chain polyhydroxyalkanoate includes the poly- hydroxyl containing 4 and 5 carbon units Base aliphatic acid such as poly 3-hydroxy butyrate, 3-hydroxybutyrate -3- hydroxyl valerates, can include Ralsonia by various bacteria Eutropha, Alcaligenes latus are synthesized.The crystallinity of this kind of polyhydroxyalkanoate is higher such as poly- 3- hydroxyls fourth The crystallinity of acid esters (PHB) can reach 70%, fusing point height (about 180 DEG C) and be closer to the decomposition temperature of PHB and be not easy thermoplastic Processing；PHB belong to high-modulus (can reach 3.5GPa) high intensity (>40MPa), but material elongation at break (about 5% or so) It is relatively low.The crystallinity (about 60%) of 3-hydroxybutyrate -3- hydroxyl valerates (PHBV) is slightly less than PHB, its fusing point is less than PHB, with The increase of hydroxypentanoic acid content in PHBV its fusing point reduction.The thermoplastic processing temperature window of PHBV is compared with PHB wide, but PHBV Crystallization rate is slower, can reach a few minutes or longer, thermoplastic processing is also relatively difficult.
Middle side chain polyhydroxyalkanoate includes for example poly- 3- hydroxyls fourth of the poly-hydroxy fatty acid containing 6 and 14 carbon units Acid -3- hydroxycaproic esters, poly- 3-hydroxybutyrate -3- Hydroxyoctanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxynonanoates, poly- 3- hydroxyls Butyric acid -3- hydroxydecanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxylauric acid esters etc., can be micro- by Pseudomonas putida etc. Biosynthesis.The fusing point of this kind of polyhydroxyalkanoate is low, and with the carbon number of middle side chain unit and the increase of content Its ductility significantly improves, and some even has the ductility of similar elastomeric body and can recover deformation.Wherein poly- 3-hydroxybutyrate- 3- hydroxycaproic esters are especially suitable for the present invention.
In order to solve the above-mentioned technical problem two, the technical solution adopted in the present invention is：One kind prepares above-mentioned technical side The thermoplastic cellulose of any graft modification with the special rheological equationm of state of case is noted with Microbe synthesis polyester blend The method for moulding product, using melt blending, the desired amount of each component is uniformly mixed in the molten state, blend is melted Body cooling granulation, blends particles are injected into a mold cavity on an injection molding machine after fusion plastification by injection screw, Blend melt in certain pressure and dwell time, injection mold is departed from after supercooling becomes injection and make in mold cavity Product.
In above-mentioned technical proposal, the desired amount of each component includes the desired amount of thermoplastic cellulose, the desired amount of microorganism Synthesizing polyester, the desired amount of reactive monomer, further preferably including the desired amount of initiator.
In above-mentioned technical proposal, thermoplastic cellulose and the Microbe synthesis polyester blend of the graft modification melt Blend method is preferably twin-screw continuous extrusion method.
In above-mentioned technical proposal, thermoplastic cellulose and the Microbe synthesis polyester blend of the graft modification melt Blend method preferably include by thermoplastic cellulose powder by continuous extruding pelletization then again with Microbe synthesis polyester, reaction Property monomer and initiator be blended according to required ratio after be added on a double screw extruder and carry out extruding pelletization.
In above-mentioned technical proposal, thermoplastic cellulose and the Microbe synthesis polyester blend of the graft modification melt Blend method preferably include by thermoplastic cellulose powder by continuous extruding pelletization then again with Microbe synthesis polyester, reaction Property monomer and initiator are dosed on a double screw extruder and carry out extruding pelletization respectively according to required feeding ratio.
In above-mentioned technical proposal, thermoplastic cellulose and the Microbe synthesis polyester blend of the graft modification melt Blend method is preferably included thermoplastic cellulose powder with Microbe synthesis polyester, reactive monomer and initiator according to certain Feeding ratio be dosed to respectively on a double screw extruder and carry out extruding pelletization.
In above-mentioned technical proposal, thermoplastic cellulose and the Microbe synthesis polyester blend of the graft modification melt The screw speed of blend method is preferably 50rpm to 1500rpm.
In above-mentioned technical proposal, thermoplastic cellulose and the Microbe synthesis polyester blend of the graft modification melt The temperature of blend method is preferably 140 DEG C to 240 DEG C.
In order to solve the above-mentioned technical problem two, it is also an option that described in another preparation above-mentioned technical proposal is any The thermoplastic cellulose of graft modification with the special rheological equationm of state and the method for Microbe synthesis polyester blend injection-molded item： Core material or blend are added on an extra quality common injection molding machine and are injected into one by injection screw after being plasticized, melting In mold cavity, the core layer that injection mold becomes injection-molded item is departed from after pressurize and cooling, by skin-material or blending Thing is added on another injection molding machine and injection, pressurize and is cooled into second mold cavity equipped with core layer Double injection product is prepared behind top layer；Wherein, at least one layer of thermoplastic fibre for graft modification of the double injection product Element and Microbe synthesis polyester blend, are all the thermoplastic cellulose and Microbe synthesis polyester blend of graft modification when two layers During thing, the thermoplastic cellulose of the graft modification in two layers has different proportion of composing from Microbe synthesis polyester blend Thermoplastic cellulose, Microbe synthesis polyester, reactive monomer and initiator.
In above-mentioned technical proposal, the double injection product core layer thickness account for double injection product gross thickness (including Core layer and top layer) 95 to 55%.
In above-mentioned technical proposal, the surface part of the double injection product and physical property, the chemistry of core Property and engineering properties etc. can be different, as surface part has than core the toughness of higher, the injection-molded item is existed It is subject to be hardly damaged under the action of external stress and impact force；Or surface part has the abrasion resistance of higher than core, the note Modeling product is hardly damaged in the case where being subject to external mechanical wear to act on.
In above-mentioned technical proposal, the core material and skin-material are entirely different with blend of the present invention Material such as low density polyethylene (LDPE), linear low density polyethylene, high density polyethylene (HDPE), polypropylene, polyolefin elastomer, the third rubber of second Glue, polyethylene terephthalate, polyamide, Polyurethane etc..
Material therefor of the present invention and preparation method are simply described below below：
1. thermoplastic cellulose
The thermoplastic cellulose of the present invention is the very wide cellulose derivative of a kind of scope, such cellulose derivative Each three hydroxylic moieties repeated on dehydrated glucose unit or all carried out being esterified or be etherified etc. the chemistry of form and changed Property.The extent index for characterizing its modification is substitution value (Degree of Substitution), it is defined as each repetition and is dehydrated The mean number substituted on glucose unit in three hydroxyls, maximum were 3.0 (3 hydroxyls are all substituted), minimum 0 (pure cellulose).
The thermoplastic cellulose ester included in the present invention include cellulose and two kinds and two or more alicyclic organic aliphatic carboxylic acids, The mixed cellulose ester that organic fatty race acid anhydrides and organic fatty race carboxylic acid halides are formed, different alicyclic organic aliphatic carboxylic acids, organic fatty The carbon number difference of race's acid anhydrides and organic fatty race carboxylic acid halides is greater than or equal to 1.
Cellulose esters is usually made by native cellulose and the reactions such as organic acid, acid anhydrides or acyl chlorides, the hydroxyl in cellulose Substitution value is from 0.5 to 2.8.Applicable cellulose ester product includes the Eastman of Eastman Chemical of U.S. productionTMAcetic acid fourth Acid cellulose ester CAB-171-15, CAB-321-0.1, CAB-381-0.1, CAB-381-0.5, CAB-381-20, CAB-485- 10, CAB-500-5, CAB-531-1 etc..Such as：Butyryl component containing 50% mass fraction, 2.8% mass in CAB-531-1 The acetyl component of fraction, the hydroxyl moieties of 1.7% mass fraction, the viscosity measured according to 1343 standards of ASTM are 5.6 pools.It is fine The plain ester of dimension has application in industries such as fiber, weaving, coating, food additives and pharmaceutical industries.In coating industry, with the addition of Coating effect can be improved after cellulose esters, including：Hardness, mobility, planarization, transparency and glossiness etc..Acetate propionate Cellulose esters (CAP) and cellulose acetate-butyrate (CAB) are two kinds of wider mixed fiber element esters of commercial use.
2. Microbe synthesis polyester
The present invention Microbe synthesis polyester by microbial fermentation processes prepare not only can be with complete biodegradable but also complete The polyester of bio-based.The Biopolvester includes homopolymer (homopolymer), i.e., the polyester formed by a kind of hydroxy fatty acid Including poly 3-hydroxy butyrate (PHB), poly- 3- hydroxyl valerates (PHV), poly- 3- hydroxycaproic esters (PHH), poly- 3- hydroxyheptanoic acids Ester, poly- 3- Hydroxyoctanoic acids ester, poly- 3- hydroxynonanoates, poly- 3- hydroxydecanoic acids ester, poly- 3- hydroxydecanoic acids ester, poly- 3- hydroxylauric acids Ester, poly- 3- hydroxyls palmitate, poly- 3- hydroxy stearic acid esters etc..
It is adapted to the Microbe synthesis polyester of the present invention to include the copolymerization formed by two or more hydroxy fatty acid Ester includes poly- 3-hydroxybutyrate -3- hydroxyl valerates (PHBV, P3HB3HV), the poly- butyric ester of 3-hydroxybutyrate -4 (P3HB4HB), poly- 3-hydroxybutyrate -3- hydroxycaproic esters (PHBHx or 3HBHx), poly- 3-hydroxybutyrate -3- hydroxyheptanoates, Poly- 3-hydroxybutyrate -3- Hydroxyoctanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxynonanoates, poly- 3-hydroxybutyrate -3- hydroxydecanoic acids Ester, poly- 3-hydroxybutyrate -3- hydroxylauric acid esters, poly- 3-hydroxybutyrate -3- hydroxyl palmitates, poly- 3-hydroxybutyrate -3- hydroxyls Base stearate；Poly- 3- hydroxypentanoic acids -3- hydroxycaproic esters, poly- 3- hydroxypentanoic acids -3- hydroxyheptanoates, poly- 3- hydroxypentanoic acids - 3- Hydroxyoctanoic acid esters, poly- 3- hydroxypentanoic acids -3- hydroxynonanoates, poly- 3- hydroxypentanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxyls penta Acid -3- hydroxylauric acid esters, poly- 3- hydroxypentanoic acids -3- hydroxyl palmitates, poly- 3- hydroxypentanoic acids -3- hydroxy stearic acid esters；It is poly- 3- hydroxycaproic acid -3- hydroxyheptanoates, poly- 3- hydroxycaproic acids -3- Hydroxyoctanoic acid esters, poly- 3- hydroxycaproic acids -3- hydroxynonanoates, Poly- 3- hydroxycaproic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxycaproic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxycaproic acids -3- hydroxylauric acids Ester, poly- 3- hydroxycaproic acids -3- hydroxyl palmitates, poly- 3- hydroxycaproic acids -3- hydroxy stearic acid esters；Poly- 3- hydroxyheptanoic acids -3- hydroxyls Base caprylate, poly- 3- hydroxyheptanoic acids -3- hydroxynonanoates, poly- 3- hydroxyheptanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxyheptanoic acids -3- Hydroxylauric acid esters, poly- 3- hydroxyheptanoic acids -3- hydroxyl palmitates, 3- hydroxyheptanoic acid -3- hydroxy stearic acid esters；Poly- 3- hydroxyls are pungent Acid -3- hydroxynonanoates, poly- 3- Hydroxyoctanoic acids -3- hydroxydecanoic acid esters, poly- 3- Hydroxyoctanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxyls Octanoic acid -3- hydroxylauric acid esters, poly- 3- Hydroxyoctanoic acids -3- hydroxyl palmitates, poly- 3- Hydroxyoctanoic acids -3- hydroxy stearic acid esters； Poly- 3- hydroxynonanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxynonanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxynonanoic acids -3- hydroxylauric acids Ester, poly- 3- hydroxynonanoic acids -3- hydroxyl palmitates, poly- 3- hydroxynonanoic acids -3- hydroxy stearic acid esters；Poly- 3- hydroxydecanoic acids -3- hydroxyls Base laurate, poly- 3- hydroxydecanoic acids -3- hydroxyl palmitates, poly- 3- hydroxydecanoic acids -3- hydroxy stearic acid esters etc..
Being particularly suitable for the Microbe synthesis polyester of the present invention includes poly 3-hydroxy butyrate, 3-hydroxybutyrate -3- hydroxyls penta Acid esters, the poly- butyric ester of 3-hydroxybutyrate -4, poly- 3-hydroxybutyrate -3- hydroxycaproic esters, poly- 3-hydroxybutyrate -3- hydroxyls are pungent Acid esters, poly- 3-hydroxybutyrate -3- hydroxynonanoates, poly- 3-hydroxybutyrate -3- hydroxydecanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxyls Laurate, poly- 3-hydroxybutyrate -3- hydroxyl palmitates, poly- 3-hydroxybutyrate -3- hydroxy stearic acid esters etc..
Microbe synthesis polyester in the present invention can be prepared by biological fermentation process such as bacterium, yeast, the carbon that can be used Source includes various saccharide compounds or lipid material such as glucose, sucrose, fructose, soybean oil, rapeseed oil etc..It is micro- in nutrient solution Then biology (such as Alcaligenes eutrophus when) can control battalion when being bred through cell division to required quantity To suppress its reproductive process, bacterium starts to have synthesized poly- the content of nitrogen, phosphorus in nutrient solution in nutrition under conditions of nitrogen, phosphorus are limited The mode of hydroxy fatty acid (polyhydroxyalkanoates, PHA) stores carbon.By after a certain period of time, in zymotic fluid Such as 10-400 g/l higher of concentration can be reached, the weight in dry bacterial cell can reach 80% or more, so Polyhydroxyalkanoate (PHA) divides from cell through the methods of broken garland cells wall (as utilized surfactant), solvent extraction afterwards Separate out and.
Polyhydroxyalkanoate can be prepared by natural microbial or by genetically modified microorganism.The classification bag of microorganism Include bacterium, yeast etc..Genetically modified plants containing pha synthesizing enzyme can also be included corn, tobacco, willow by polyhydroxyalkanoate Branch millet (switchgrass) synthesis, the genetically modified plants of harvest collect polyhydroxyalkanoate by solvent extraction.
Polyhydroxyalkanoate includes short-side chain polyhydroxyalkanoate and middle side chain polyhydroxyalkanoate.Short-side chain gathers Hydroxy fatty acid includes such as poly 3-hydroxy butyrate of the poly-hydroxy fatty acid containing 4 and 5 carbon units, and 3-hydroxybutyrate- 3- hydroxyl valerates, can be synthesized by various bacteria including Ralsonia eutropha, Alcaligenes latus.This is a kind of The higher crystallinity such as poly 3-hydroxy butyrate (PHB) of crystallinity of polyhydroxyalkanoate can reach 70%, fusing point is high (about 180 DEG C) and it is closer to the decomposition temperature of PHB and is not easy thermoplastic processing；It is high-strength that PHB belongs to high-modulus (can reach 3.5GPa) Degree (>40MPa), but material elongation at break (about 5% or so) it is relatively low.3-hydroxybutyrate -3- hydroxyl valerates (PHBV) Crystallinity (about 60%) is slightly less than PHB, its fusing point is less than PHB, and with the increase of hydroxypentanoic acid content in PHBV, its fusing point reduces. The thermoplastic processing temperature window of PHBV is compared with PHB wide, but the crystallization rate of PHBV is slower, can reach a few minutes or longer, heat Modeling processing is also relatively difficult.
Middle side chain polyhydroxyalkanoate includes for example poly- 3- hydroxyls fourth of the poly-hydroxy fatty acid containing 6 and 14 carbon units Acid -3- hydroxycaproic esters, poly- 3-hydroxybutyrate -3- Hydroxyoctanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxynonanoates, poly- 3- hydroxyls Butyric acid -3- hydroxydecanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxylauric acid esters etc., can be micro- by Pseudomonas putida etc. Biosynthesis.The fusing point of this kind of polyhydroxyalkanoate is low, and with the carbon number of middle side chain unit and the increase of content Its ductility significantly improves, and some even has the ductility of similar elastomeric body and can recover deformation.Wherein poly- 3-hydroxybutyrate- 3- hydroxycaproic esters are especially suitable for the present invention.3. reactive monomer
Heretofore described reactive monomer is the vinyl compound with polar group, the polar group bag Include but be not limited to：Hydroxyl, carboxyl, carbonyl, ester group, amino, sulfydryl, sulfonic group, ehter bond, halogen, peptide bond, anhydride bond etc..Institute The reactive monomer stated can react with other components in blend under certain condition, and then be grafted to covalent bond In other components, special modified effect is played.
Preferable reactive monomer is maleic acid anhydride in the present invention, acrylic compounds, methacrylic, acrylate At least one of compounds such as class, methyl acrylic ester, acrylic amide, methacryl amine.Preferred reaction Property monomer is methyl acrylic ester, in such as hydroxyethyl methacrylate (HEMA), glycidyl methacrylate (GMA) At least one.
4. initiator
Heretofore described initiator is radical initiator, its having of generating free radicals of decomposable asymmetric choice net under certain condition Machine compound, including but not limited to：Acyl peroxide, such as benzoyl peroxide (BPO)；Alkyl (dialkyl group) peroxidating Thing, such as dual-tert-butyl peroxide, double cumyl peroxides, cumyl peroxy butyl, 3,3,5- 3-methyl cyclohexanols Alkane -1,1- diperoxies the tert-butyl group, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes etc.；Perester, such as crosses trimethylace tonitric uncle Butyl ester, mistake -2 ethyl hexanoic acid tert-butyl ester, t-butyl perbenzoate, peroxidating lauric acid etc.；Alkyl peroxide, such as tertiary fourth Base hydrogen peroxide, isopropyl benzene hydroperoxide etc.；Ketone peroxide, such as methyl ethyl ketone peroxide；Azo compound, such as two isobutyl of azo Cyanogen (AIBN) etc..
It is preferably benzoyl peroxide to be suitable for the invention initiator, azo-bis-isobutyl cyanide, cumyl peroxide, mistake Aoxidize in di-t-butyl, tert-butyl hydroperoxide, perbenzoic acid, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes etc. At least one.Preferred initiator is benzoyl peroxide, in 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes extremely Few one kind.
5. the thermoplastic cellulose of graft modification and Microbe synthesis polyester blend
The blend that the present invention announces is by a kind of thermoplastic cellulose, a kind of biodegradable Microbe synthesis polyester, A kind of reactive monomer and a kind of initiator composition, wherein the thermoplastic cellulose containing 20 to 80 mass parts, 80 to 20 quality The initiator of the Microbe synthesis polyester of part, the reactive monomer of 0.1 to 10 mass parts and 0.01 to 1 mass parts.The blend In addition to comprising above component, following at least one additive is further included：Compatibility agent, inorganic filler, antioxidant, lubricant, Colouring agent etc..
Many physico-chemical properties (such as melt viscosity, melt index) of blend polymer are mainly by forming its polymer Species and proportion of composing determine.Type of polymer essentially dictates the " compatibility between blend component (compatibility) ", compatibility is that one to interact between different polymer measures, and is made when between different polymer It is known as (miscible) system of dissolving each other when stable and uniform on molecular scale mixes with it relatively by force, can be made；Other polymer Between interaction it is slightly weak, although cannot dissolve each other in molecular scale, but still can be in nanoscale or micro-meter scale stable and uniform Scattered, this kind of blend is referred to as compatible (compatible) system；Interact between other polymer very weak, even if by Forced Mixing, they also tend to form respective phase region, and this kind of blend is then incompatible (incompatible) system.No Different component has obvious phase separation in compatible system, that is, forms phase-separation system (phase separated system).It is poly- Compound blend glass transition temperature (" Tg") information simple can judge as one of compatibility quality between each component Foundation【《Multicomponent polymeric-principle, structure and performance》, kingdom, which builds, writes, and 2013, p.20-22】If blend is protected respectively Hold the glass transition temperature of raw material components, then compatibility is bad between showing component, and when blend only has a vitrifying During transition temperature, then compatibility is preferable between showing component.In the case where type of polymer determines, some physics and chemistry of blend There are certain functional relation with its proportion of composing for property (such as melt viscosity, melt index)【《The plastic engineering handbook first volume》, Huang Rui is edited, and 2000, p.633-637；Melt Rheology of Polymer Blends from Melt Flow Index, International Journal of Polymeric Materials,1984,10,p.213-235】, people can be accordingly Substantially speculate even blend of the design with special properties.In the bad co-mixing system of some compatibilities, it may occur however that altogether Mixed thing viscosity is less than the situation of raw material components【《JRG-Fourth statistics》, Jin Riguang work, 1998, p.630-633】, there is the phenomenon The reason for there is no final conclusion at present, overall viscosity declines after the interface sliding that one of which is construed between different phases causes mixing. Similar phenomenon has not been reported in the preferable blend system of compatibility, if more than being used in the preferable system of compatibility Phenomenon, must there is great potentiality.
Also containing hydroxyethyl methacrylate, glycidyl methacrylate etc. in the blend composition that the present invention announces With the good reactive monomer and initiator of the blending main component compatibility of thing, the reactive monomer with common plasticizer not Together, it has higher reactivity, in the presence of high-rate of shear, high melt temperature (more than 200 DEG C) and initiator In double screw extruder, radical reaction easily occurs, reactive monomer can be grafted on any C-H in blend component in theory On key (Fig. 1 and the structure diagram that Fig. 2 is two kinds of possible generations in the present invention), its effect differs markedly from plasticizer, and After reactive extrursion, unreacted monomer can be removed in devolatilization processes, therefore reactive monomer simply is considered as plasticizer The decline of explanation mixed system viscosity is simultaneously invalid.Not only addition is seldom for initiator, and it easily decomposes be produced from high temperature It is consumed by base.After reactive grafting, due to grafted monomers, there are between thermoplastic cellulose and Biodegradable polyester The interaction blend non-grafted compared to same composition can be stronger.In conclusion the graft modification that the present invention announces Thermoplastic cellulose and Microbe synthesis polyester blend the special rheological equationm of state, led by the Specific Interactions between component Cause, and the compatibility between this mixed system component is good, in compatible co-mixing system, viscosity reduces after mixing phenomenon compared with Few, also few documents and materials have related report.
There is the property that a variety of methods can describe blend, addition rule is wherein simplest one kind.Advised using addition It then can substantially speculate the theory property of some polyblends, its addition theory can be expressed (herein only with equation below Consider key component, ignore component of the content below 2%)：
P=c1P1+c2P2
P be blend property, c1And P1For the concentration and property of component 1；c2And P2For the concentration and property of component 2.This The thermoplastic cellulose of invention and the property (P) of Microbe synthesis polyester blend, such as apparent melt viscosity, melt index can To calculate the numerical value of theoretical prediction using addition rule, that is, it is defined as " addition theoretical value ", which can detect with experiment Apparent viscosity, the numerical value such as melt index compares.The concentration of component can use mass fraction or volume fraction to express, the present invention Selection calculates theoretical numerical value with mass fraction.
The blend composition of the concrete embodiment of the present invention includes the thermoplasticity acetate butyrate fiber of 20 to 80 mass parts Plain ester, the poly 3-hydroxy butyrate of 80 to 20 mass parts or poly- 3-hydroxybutyrate -3- hydroxyl valerates or poly- 3-hydroxybutyrate -3- The Microbe synthesis polyester such as hydroxycaproic ester, the hydroxyethyl methacrylate or Glycidyl methacrylate of 0.1 to 10 mass parts are sweet The benzoyl peroxide or double two or five grade initiators of grease isoreactivity monomer and 0.01 to 1 mass parts, it is characterised in that blending The melt viscosity of thing is in low shear rate (100s-1) under the conditions of it is at least lower than the mixing addition theoretical value of two kinds of predominant starting materials 50%.The melt viscosity of some blends more preferably formed is in low shear rate (100s-1) under the conditions of starting main than two kinds The mixing addition theoretical value at least low 65% of raw material；Some most preferred groups into blend melt viscosity in low shear rate (100s-1) under the conditions of it is at least lower by 70% than the mixing addition theoretical value of two kinds of predominant starting materials.
The blend composition of the concrete embodiment of the present invention includes the thermoplasticity acetate butyrate fiber of 20 to 80 mass parts Plain ester, the poly 3-hydroxy butyrate of 80 to 20 mass parts or poly- 3-hydroxybutyrate -3- hydroxyl valerates or poly- 3-hydroxybutyrate -3- The Microbe synthesis polyester such as hydroxycaproic ester, the hydroxyethyl methacrylate or Glycidyl methacrylate of 0.1 to 10 mass parts are sweet The benzoyl peroxide or double two or five grade initiators of grease isoreactivity monomer and 0.01 to 1 mass parts, it is characterised in that blending The melt viscosity of thing is in high-rate of shear (1363s-1) under the conditions of than two kinds of predominant starting materials mixing addition theoretical value at least Low 45%.The melt viscosity of some blends more preferably formed is in high-rate of shear (1363s-1) under the conditions of main than two kinds rise The mixing addition theoretical value at least low 60% of beginning raw material；Some most preferred groups into blend melt viscosity in high-rate of shear (1363s-1) under the conditions of it is at least lower by 65% than the mixing addition theoretical value of two kinds of predominant starting materials.
The blend composition of the concrete embodiment of the present invention includes the thermoplasticity acetate butyrate fiber of 20 to 80 mass parts Plain ester, the poly 3-hydroxy butyrate of 80 to 20 mass parts or poly- 3-hydroxybutyrate -3- hydroxyl valerates or poly- 3-hydroxybutyrate -3- The Microbe synthesis polyester such as hydroxycaproic ester, the hydroxyethyl methacrylate or Glycidyl methacrylate of 0.1 to 10 mass parts are sweet The benzoyl peroxide or double two or five grade initiators of grease isoreactivity monomer and 0.01 to 1 mass parts, it is characterised in that blending The melt index of thing is at least higher by about 90% than the mixing addition theoretical value of two kinds of predominant starting materials.What some were more preferably formed is total to The melt index of mixed thing is at least higher by 200% than the mixing addition theoretical value of two kinds of predominant starting materials；Some most preferred groups into The melt index of blend is at least higher by 300% than the mixing addition theoretical value of two kinds of predominant starting materials.
The blend " unusually " formed by a certain percentage of the present invention, " unexpectedly " have more former than main starting Material：Pure thermoplastic cellulose and Microbe synthesis polyester starting material mixes the lower apparent shear viscosity of addition theoretical value, " concave " curve is presented i.e. in " apparent viscosity-composition " graph of a relation, shows as " melt viscosity trap " (Melt Viscosity Well) phenomenon, shows that the blend has " anti-synergistic effect " (Antagonistic Effect or Anti- of apparent viscosity Synergistic Effect)。
The blend " unusually " formed by a certain percentage of the present invention, " unexpectedly " have more former than main starting Material：Melt index (the MFR of the mixing addition theoretical value higher of pure thermoplastic cellulose and Microbe synthesis polyester starting material： Melt Flow Rate), i.e., in " melt index-composition " graph of a relation, " convex " curve is presented, shows as " melt index Peak " (MFR Peak) phenomenon, shows that the blend has " cooperative effect " (the Synergistic Effect) of melt index.
6. prepare the method for the thermoplastic cellulose and Microbe synthesis polyester blend of graft modification
A kind of thermoplastic cellulose for preparing graft modification of the present invention and the method for Microbe synthesis polyester blend.Should Method in a continuous process the desired amount of thermoplastic cellulose, it is the desired amount of Microbe synthesis polyester, the desired amount of anti- Answering property monomer and the desired amount of initiator are uniformly mixed in the molten state, and extruding pelletization, and prepared blend is special Sign is its melt viscosity in low shear rate (100s-1) under the conditions of than two kinds of predominant starting materials blending addition theoretical value extremely Few low 50%；In high-rate of shear (1363s-1) under the conditions of it is at least lower than the blending addition theoretical value of two kinds of predominant starting materials 45%, and the melt index of the blend is at least higher by about 90% than the blending addition theoretical value of two kinds of predominant starting materials.
The continuous fusion preparation method of the present invention includes two-step method and one-step method.In two-step method, thermoplastic cellulose powder End first passes around single screw rod or double screw extruder and is granulated, then thermoplastic fibre crude granule, Microbe synthesis polyester granulate, Reactive monomer and initiator are according to a certain percentage after mixing, then with a feeding machine according to certain feed rate addition To the spout of a double screw extruder.Feeding machine can be that weight-loss type feeding machine can also be volume type feeding machine.It is another A concrete embodiment is respectively that thermoplastic fibre crude granule, Microbe synthesis polyester granulate, reactivity is single using multiple feeding machines Body and initiator are dosed to progress reactive extrursion granulation on a double screw extruder respectively according to certain feeding ratio.
The one-step method of the present invention is granulated thermoplastic fibres element powder without hot-working and is directly pressed using a feeding machine Certain feed rate is added into the spout of double screw extruder, at the same Microbe synthesis polyester granulate, reactive monomer and Initiator is added into the spout of double screw extruder with other feeding machines by certain feed rate, carries out twin-screw extrusion, Batten is extruded through water-carrying groove or underwater cutpellet, prepares blends particles.Extrudate can also with anhydrous process by it is air-cooled then Pelletizing.
The extrusion temperature for being suitable for the present invention is preferably 140 DEG C and divides to the heat of thermoplastic cellulose and Microbe synthesis polyester The low person of temperature is solved, preferred extrusion temperature is 140 DEG C to 240 DEG C.The rotating speed of extruder is preferably 50rpm to 1500rpm, more Preferably 100rpm to 800rpm.
Being suitable for the invention melt blending equipment has many kinds to include kneading machine, Farrel continuous mixers, Banbury Mixer, single screw extrusion machine, double screw extruder, multi-screw extruder (more than two screw rod), reciprocating Single screw extrusion Machine such as Buss co-kneader (Buss Ko-Kneader) etc..Preferable method includes double spiral shells for continuous fusion blending extrusion method Bar extrusion method.Being suitable for the invention continuous twin-screw and squeezing machine includes the double screw extruder of different designs, such as Germany ZSK Mcc18 equidirectional parallel double-screw extruders of Coperion productions etc..
The thermoplastic cellulose of graft modification prepared by the method for twin-screw continuous fusion that the present invention is shown coextrusion with Microbe synthesis polyester blend has the low melt viscosity of " unexpected ".A kind of embody of the present invention is in the same terms Under, the melt viscosity of blend is less than the mixing addition theoretical value of thermoplastic cellulose and Microbe synthesis polyester starting material. The viscosity, which reduces, has generality, is included in compared with low shear rate such as 100s-1With in higher shear rate such as 1363s-1. 100s-1Under shear rate, the melt viscosity of its blend is at least lower than the mixing addition theoretical value of two kinds of predominant starting materials 50%.Some more preferably form (the Microbe synthesis polyester of 50 to 20 mass parts and the thermoplastic cellulose of 50 to 80 mass parts, Reactive monomer is 2 to 8 mass parts, and initiator is 0.05 to 0.2 mass parts) the melt viscosity of blend main than two kinds rise The mixing addition theoretical value at least low 65% of beginning raw material, some most preferred groups are into (the Microbe synthesis polyester of 35 mass parts and 65 The thermoplastic cellulose of mass parts, reactive monomer are 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts) blending The melt viscosity of thing is at least lower by 70% than the mixing addition theoretical value of two kinds of predominant starting materials.In 1363s-1Under shear rate, The melt viscosity of blend is at least lower by 45% than the mixing addition theoretical value of two kinds of predominant starting materials, some are more preferably formed (the Microbe synthesis polyester of preferably 50 to 20 mass parts and the thermoplastic cellulose of 50 to 80 mass parts, reactive monomer for 2 to 8 mass parts, initiator are 0.05 to 0.2 mass parts) mixing of the melt viscosity than two kinds of predominant starting materials of blend add Into theoretical value at least low 60%, some most preferred groups are into (the Microbe synthesis polyester of 35 mass parts and the thermoplasticity of 65 mass parts Cellulose, reactive monomer are 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts) blend melt viscosity ratio The mixing addition theoretical value at least low 65% of two kinds of predominant starting materials.
The thermoplastic fibres element and one kind of Microbe synthesis polyester blend material of graft modification prepared by the present invention are specific Embodiment is mixing addition theoretical value of the melt index higher than two kinds of predominant starting materials of blend.The blend preferably constituted Melt index more preferably forms (50 to 20 quality higher than the mixing addition theoretical value at least about 90% of two kinds of predominant starting materials Part Microbe synthesis polyester and 50 to 80 mass parts thermoplastic cellulose, reactive monomer is 2 to 8 mass parts, initiator For 0.05 to 0.2 mass parts) blend melt index higher than two kinds of predominant starting materials mixing addition theoretical value at least 200%, most preferred group is into (the Microbe synthesis polyester of 35 mass parts and the thermoplastic cellulose of 65 mass parts, reactive monomer For 2 to 6 mass parts, initiator is 0.075 to 0.15 mass parts) the melt index body of blend can be higher than two kinds and main rise The mixing addition theoretical value at least 300% of beginning raw material.
7. prepare the method for the thermoplastic cellulose and Microbe synthesis polyester blend injection-molded item of graft modification
The present invention announces a kind of thermoplastic cellulose for preparing the graft modification with the special rheological equationm of state and is closed with microorganism Into the method for polyester blend injection-molded item, it is characterised in that the blend by 20 to 80 mass parts thermoplastic cellulose, 80 To the Microbe synthesis polyester of 20 mass parts, the initiator group of the reactive monomer of 0.1 to 10 mass parts and 0.01 to 1 mass parts Into.The continuous fusion extrusion blending method of the blend by mentioned earlier is prepared.The melt viscosity of blend is in low sheraing speed Rate (100s-1) under the conditions of it is at least lower by 50% than the addition theoretical value of two kinds of primary raw materials；In high-rate of shear (1363s-1) condition The lower addition theoretical value than two kinds of primary raw materials is at least low by 45%.Blend has more preferable injection molding than predominant starting material Performance, in this method blend be plasticized on an injection molding machine, melt after be injected into by injection screw in a mold cavity, altogether Mixed thing melt in certain pressure and dwell time, injection mold is departed from after supercooling becomes injection and make in mold cavity Product.
In injection molding process, blend of the invention is added to a screw-type injection machine by a loading hopper, The cylinder of injector is heated to certain temperature by electric heating system, and the temperature of suitable injector cylinder is 160 DEG C to 240 DEG C, the temperature being more suitable for is 180 DEG C to 220 DEG C.
In an injection circulation, the thermal energy that injector is provided by the rotating mechanical energy of screw rod and heating cylinder is altogether Mixed thing plasticizing and fusing, and be injected into the blend melt of certain mass with certain pressure and speed within the regular hour In one mold cavity having been switched off；Screw rod continues to pressure and continues to keep certain pressure (pressurize pressure after injection Power), injection-molded item shrinkage phenomenon is avoided to increase the density of blend melt, suitable dwell pressure is 5 bars (bar) (0.5MPa) to 2000 bars (200MPa).Then mould enters cooling stage, cools down by being flowed in the cooling line in injection mold Dynamic coolant (water or other liquid) is completed, and suitable mold temperature is 5 DEG C to 100 DEG C, and more preferable mold temperature is 10 DEG C To 80 DEG C, best mold temperature is 20 DEG C to 60 DEG C,.Cooling time in a mold is 1 second to 200 seconds, preferably cooling Time is 5 seconds to 100 seconds, and best cooling time is 10 seconds to 80 seconds.Injection-molded item after cooling is at ejector beam (ejector) Under the action of break away from moulds.
The blend injection-molded item of the present invention includes different size and dimensions.The blend of the present invention is special due to its The rheological equationm of state can prepare very thin injection-molded item.The preferred thickness of the injection-molded item of the present invention is 100 microns to 50 millimeters, The thickness of injection-molded item is 250 microns to 25 millimeters in some concrete embodiments, also has injection-molded item in some concrete embodiments Thickness is 500 microns to 5 millimeters.
The injection-molded item of the present invention includes individual layer injection-molded item and double-deck or multi-layer injection molding product.Include in double injection machine Two independent adapted to injection system：1) injection molding machine is responsible for injecting the core of double injection product, which can note Penetrate the blend with the special rheological equationm of state of the present invention；2) injection molding machine is responsible for injecting the skin section of double injection product Point, thermoplastic skin layer material be added in this injection molding machine and in second mold cavity equipped with core layer injection, Pressurize and it is cooled into preparing double injection product behind top layer.Wherein the surface part can be the present invention special blend but It is different with the core composition of injection-molded item, such as surface part can be the thermoplastic cellulose containing 20 mass parts With the Microbe synthesis polyester and the desired amount of reactive monomer and initiator of 80 mass parts；Contain 60 mass parts in core Thermoplastic cellulose and 40 mass parts Microbe synthesis polyester and the desired amount of reactive monomer and initiator；Another Concrete embodiment be the skin-material be with the entirely different material of the present invention for example low density polyethylene (LDPE), linear low density polyethylene, High density polyethylene (HDPE), polypropylene, polyolefin elastomer, EP rubbers, polyethylene terephthalate, polyamide, Polyurethane Deng.
Core layer thickness accounts for the 95 of double injection product gross thickness (including core layer and top layer) and arrives in double injection product 55%.Core layer thickness accounts for 90 to the 60% of double injection product gross thickness in preferred double injection product.It is further excellent Core layer thickness accounts for 80 to the 65% of double injection product gross thickness in the double injection product of choosing.
Due to the difference of composition, the surface part of the injection-molded item and physical property of core, chemical property and machinery Property etc. is also different, and one concrete embodiment of the present invention is that the surface part of injection-molded item has the tough of higher than core Degree, the injection-molded item are hardly damaged under the action of external stress and impact force is subject to.Another concrete embodiment is injection-molded item Surface part have the abrasion resistance of higher than core, the injection-molded item not rapid wear in the case where being subject to external mechanical wear to act on It is bad.Multi-layer injection molding product, which has to have than individual layer injection-molded item, to be more widely applied.By preparing double-deck injected articles, Wo Menke Effectively to introduce the thermoplastic cellulose material of green low-carbon in injection-molded item.The twin-screw extrusion of blend injection-molded item Temperature is 140 DEG C to 240 DEG C, and preferable extrusion temperature is 160 DEG C to 220 DEG C.The revolution of double screw extruder arrives for 10 500rpm, preferable rotating speed arrive 300rpm for 20.
The graft modification with the special rheological equationm of state that the continuous extrusion blend method announced using the present invention is prepared Thermoplastic cellulose and Microbe synthesis polyester blend injection-molded item, there are than two kinds predominant starting material mixing additions reasons By lower melt viscosity is worth, the melt index of higher, is more preferably molded performance, the note suitable for preparing large volume, thin-walled thickness Product is moulded, there is wide application potential, achieve preferable technique effect.
Brief description of the drawings
A kind of structure diagrams of possible HEMA graft modifications PHBV (PHBV-g-HEMA) of Fig. 1.
A kind of structure diagrams of possible HEMA graft modifications CAB (CAB-g-HEMA) of Fig. 2.
At 180 DEG C of Fig. 3, the relation of each mixture particle apparent shear viscosity and shear rate.
At 180 DEG C of Fig. 4, each mixture particle is in 100s-1Shear rate under, the pass between apparent shear viscosity and composition It is that dotted line is the addition theoretical calculation numerical value line of PHBV and CAB in figure.
At 180 DEG C of Fig. 5, each mixture particle is in 1363s-1Shear rate under, the pass between apparent shear viscosity and composition It is that dotted line is the addition theoretical calculation numerical value line of PHBV and CAB in figure.
The DSC temperature lowering curves of each mixture particles of Fig. 6.
Second of heating curve of DSC of each mixture particles of Fig. 7.
Each mixture particle glass transition temperatures of Fig. 8 and the relation of composition.
The TGA curves of each mixture particles of Fig. 9 in air atmosphere.
Relation between the melt index (190 DEG C, 2.16kg) of each mixture particles of Figure 10 and composition, dotted line is in figure The addition theoretical calculation numerical value line of PHBV and CAB.
The pattern of each blend injection battens of Figure 11.
The present invention carries out performance measurement by the following method：
Melt index (MFR) assay method：By 1133 standards of ISO, melted using Lloyd Davenport MFI-10/230 Melt Index Instrument measure, 190 DEG C, weight loading 2.16kg, port mould diameter 2.095mm of barrel temperature, length 8mm, preheating time For 4min, sample is cut automatically every setting time, take 5 times and average, represent to measure with the grams of every 10 minutes (g/10min) As a result.
Rheological behaviour assay method：Using Malvern Instruments Rosand RH7 thermal high capillary rheometers Measure, processing software is Launch8.60 version.The sensor and 16/ that pressure is 10000Psi is selected in test 1.0/180 circular hole capillary die.It is compacted when filling sample for filling in batches, the precompressed by 0.5MPa twice is needed before test With the warm of 2 minutes, with ensure particle at a temperature selected (180 DEG C) completely melting and compacting.
Thermogravimetric analysis (TGA)：Test is enterprising in the Discovery series thermogravimetric analyzers of TA Instruments companies OK, it is TA Instruments Trios 3.1.4 editions to handle software.The temperature stabilization for needing to wait balance cavity before test is 40 ℃.During test, weigh 5~10mg samples and be placed in ceramic crucible, tested in the air atmosphere that flow velocity is 20mL/min, Temperature elevating range is 30~600 DEG C, and heating rate is 10 DEG C/min.
Thermal performance analysis (DSC)：Test the Discovery series of differential scanning amounts in the production of TA Instruments companies Carried out on hot instrument (DSC), processing software is TA Instruments Trios 3.1.5 editions, which is furnished with TA 90 mechanical refrigeration annexes of Refrigerated Cooling System.Measurement atmosphere is the nitrogen of 50mL/min, needed for test Sample size is 5~10mg.Test program is as follows：First by temperature stabilization at 40 DEG C, then 250 DEG C and constant temperature are warming up to 10 DEG C/min 2min removes thermal history, cools to -70 DEG C with 10 DEG C/min afterwards, is then warming up to 250 DEG C with 10 DEG C.Record temperature-fall period with And second of temperature-rise period, with the hot property of study sample.Tested by DSC, there can be the crystallization that software immediately arrives at sample Temperature (" Tc"), melting temperature (" Tm"), glass transition (" Tg"), the information such as heat content change (" △ H ").
Embodiment
The present invention is specifically described by the following examples.Herein it is important to point out that once embodiment is only right It is further described in the present invention, it is impossible to be interpreted as limiting the scope of the invention, the those of skill in the art in the field Some nonessential modifications and adaptations can be made according to foregoing invention content.
【Comparative example 1】
Used poly- 3-hydroxybutyrate -3- hydroxyl valerates (PHBV) are limited by Ningbo Tian An biotechnology in the present invention Company produces, trade mark ENMATTMY1000P.Raw material ENMATTMY1000P PHBV particles, with U.S. Thermo Fisher PolyLab HAAKE Rheomex OS PTW16 parallel dual-screw extruding machines (the screw diameter 16mm, L/D=of scientific ＆ technical corporation 40) extruding pelletization, as a comparison case.Totally 11 sections from spout to mouth mold, numbering 1-11, wherein paragraph 1 only rise the extruder To the effect of charging, can not heat.The subsidiary volume type particle feeder of extruder, is used for ENMAT after calibrationTM Y1000P PHBV raw materials are fed in twin-screw, blanking velocity 1600g/hr.The temperature that 2-11 sections of extruder is respectively：160 DEG C, 170 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature is at 206 DEG C or so, and moment of torsion is in 48.5-60%.The extruder is furnished with the circle of a diameter of 3mm After water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter from die extrusion for mouth mold, batten.Particle is collected, After taking out 4hr in 60 DEG C of vacuum drying chambers, encapsulation is spare.Melt index of the particle under 190 DEG C, 2.16kg is 21.3g/ 10min。
【Comparative example 2】
Used cellulose acetate-butyrate (CAB) is by U.S. Eastman in the present inventionTMCompany produces, and the trade mark is EastmanTMCAB-381-0.5.Raw material EastmanTMCAB-381-0.5 powder, it is public with U.S. Thermo Fisher science and technology PolyLab HAAKE Rheomex OS PTW16 parallel dual-screw extruding machines (screw diameter 16mm, the L/D=40) extrusion of department It is granulated, as a comparison case.For the extruder totally 11 sections from spout to mouth mold, numbering 1-11, wherein paragraph 1 only serve charging Effect, can not heat.The subsidiary volume type powder feeder of extruder, is used for Eastman after calibrationTM CAB- 381-0.5 raw materials are fed in twin-screw, blanking velocity 1600g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, stablizes Afterwards, melt temperature is at 198 DEG C or so, and moment of torsion is in 50-54.5%.The extruder be furnished with a diameter of 3mm circular mouth mold, batten from Die extrusion is cut into the cylindrical particle of 3mm or so with pelleter after water-bath cooling.Particle is collected, is done in 60 DEG C of vacuum After taking out 4hr in dry case, encapsulation is spare.Melt index of the particle under 190 DEG C, 2.16kg is 8.7g/10min.
【Embodiment 1】
The grafted monomers hydroxyethyl methacrylate (HEMA) that the present invention uses is Tokyo HuaCheng Industry Co., Ltd (TCI) Analysis net product, dosage is the 2% of PHBV and CAB gross masses.Two uncles of initiator 2,5- dimethyl -2,5- that the present invention uses (double two or five) are the analysis net product of lark prestige Science and Technology Ltd. to butyl peroxy hexane, and dosage is the 5% of HEMA dosages, i.e., PHBV and the 1 ‰ of CAB gross masses.By ENMATTMY1000P PHBV and EastmanTMCAB-381-0.5 is according to 4:1 quality Than, and the desired amount of HEMA and double 25 are added, stir, in PolyLab HAAKE Rheomex mentioned above Melt blending extruding pelletization in OS PTW16 parallel dual-screw extruding machines.In the paragraph 1 of extruder, calibrated volume type particle Feeder is used for the feeding of stuff and other stuff, and speed is：1600g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, stablizes Afterwards, melt temperature is at 205 DEG C or so, and moment of torsion is in 32.5-36%.The extruder be furnished with a diameter of 3mm circular mouth mold, batten from Die extrusion passes through water-bath cooling, and batten hardening by cooling speed is slower, need to collect after its fully hardened (about 15 minutes), with cutting Cylindrical particle of the grain machine-cut into 3mm or so.Particle is collected, after taking out 4hr in 60 DEG C of vacuum drying chambers, encapsulation is spare.The grain Melt index of the son under 190 DEG C, 2.16kg is 35.5g/10min.Feed intake more than and processing conditions, except some are secondary Beyond reaction, the PHBV of HEMA graft modifications can be generated in system (Fig. 1 is a kind of possible PHBV-g-HEMA structure diagrams) And/or a kind of CAB structures (Fig. 2 is possible CAB-g-HEMA structure diagrams) of HEMA graft modifications, to a certain extent While increasing component molecular amount, moreover it is possible to strengthen the compatibility between component and interaction.
【Embodiment 2】
By ENMATTMY1000P PHBV and EastmanTMCAB-381-0.5 is according to 13:7 mass ratio, and add institute The HEMA of requirement and double 25, stirs, same in PolyLab HAAKE Rheomex OS PTW16 mentioned above The melt blending extruding pelletization into double screw extruder.In the paragraph 1 of extruder, calibrated volume type particle feeder by with In the feeding of stuff and other stuff, speed is：1600g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature Degree is at 205 DEG C or so, and moment of torsion is in 28-32%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten is passed through from die extrusion Water-bath cooling is crossed, batten hardening by cooling speed is slower, need to collect after its fully hardened (about 45 minutes), is cut into pelleter The cylindrical particle of 3mm or so.Particle is collected, after taking out 4hr in 60 DEG C of vacuum drying chambers, encapsulation is spare.The particle is 190 DEG C, the melt index under 2.16kg is 48.1g/10min.
【Embodiment 3】
By ENMATTMY1000P PHBV and EastmanTMCAB-381-0.5 is according to 1:1 mass ratio, and needed for addition The HEMA of amount and double 25, stirs, in the same direction in PolyLab HAAKE Rheomex OS PTW16 mentioned above Melt blending extruding pelletization in double screw extruder.In the paragraph 1 of extruder, calibrated volume type particle feeder is used for The feeding of stuff and other stuff, speed are：1600g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃,180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature At 204 DEG C or so, moment of torsion is in 27-31%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten passes through from die extrusion After water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, 4hr is taken out in 60 DEG C of vacuum drying chambers Afterwards, encapsulate spare.Melt index of the particle under 190 DEG C, 2.16kg is 54.0g/10min.
【Embodiment 4】
By ENMATTMY1000P PHBV and EastmanTMCAB-381-0.5 is according to 7:13 mass ratio, and add institute The HEMA of requirement and double 25, stirs, same in PolyLab HAAKE Rheomex OS PTW16 mentioned above The melt blending extruding pelletization into double screw extruder.In the paragraph 1 of extruder, calibrated volume type particle feeder by with In the feeding of stuff and other stuff, speed is：1600g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature Degree is at 204 DEG C or so, and moment of torsion is in 27-34%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten is passed through from die extrusion After crossing water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, 4hr is taken out in 60 DEG C of vacuum drying chambers Afterwards, encapsulate spare.Melt index of the particle under 190 DEG C, 2.16kg is 52.8g/10min.
【Embodiment 5】
By ENMATTMY1000P PHBV and EastmanTMCAB-381-0.5 is according to 1:4 mass ratio, and needed for addition The HEMA of amount and double 25, stirs, in the same direction in PolyLab HAAKE Rheomex OS PTW16 mentioned above Melt blending extruding pelletization in double screw extruder.In the paragraph 1 of extruder, calibrated volume type particle feeder is used for The feeding of stuff and other stuff, speed are：1600g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃,180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature At 204 DEG C or so, moment of torsion is in 27-32.5%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten is passed through from die extrusion After crossing water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, 4hr is taken out in 60 DEG C of vacuum drying chambers Afterwards, encapsulate spare.Melt index of the particle under 190 DEG C, 2.16kg is 42.6g/10min.
【Embodiment 6】
7 kinds of particles of all of the above, including comparative example 1-2 and embodiment 1-5, in Malvern Instruments Rheological behaviour measure is carried out on Rosand RH7 thermal high capillary rheometers, test method is as described above.At 180 DEG C The apparent shear viscosity of each particle and the relation of shear rate are shown in Fig. 3.Its medium shear rate is in 100s-1And 1363s-1Under table See shear viscosity and the relation of composition is shown in Fig. 4 and Fig. 5 respectively, concrete numerical value is listed in Tables 1 and 2.
Obvious shear shinning phenomenon as can see from Figure 3, i.e. the bigger shear viscosity of shear rate is smaller, this phenomenon It is very common in polymeric system, show that the fundamental property of system after being blended does not have significant change.The apparent shearing of mixture Viscosity all under the same conditions ENMAT substantiallyTMY1000P PHBV and EastmanTMBelow CAB-381-0.5, that is, after mixing System viscosity is decreased obviously.Specifically see Fig. 4 and Fig. 5, can find that the apparent shear viscosity of particle after being blended is all purer than any one Starting material is all small, and viscograph is into " concave " i.e. unexpected " viscosity trap " phenomenon, and no matter is the particle after this explanation blending Viscosity diminishes under high speed or low velocity shear.
Hydroxyethyl methacrylate (HEMA) is added in entirety as small molecule can be considered a kind of plasticizer, but HEMA with Common plasticizer is different, it has higher reactivity, in high-rate of shear, high melt temperature (more than 200 DEG C) and draws In double screw extruder in the presence of hair agent double 25, radical reaction easily occurs, reactive monomer can be grafted in theory In blend component on any c h bond (Fig. 1 and the structure diagram that Fig. 2 is two kinds of possible generations in the present invention), it is clear that letter It is single that HEMA is considered as plasticizer to explain that mixed system viscosity declines and invalid.Double 25 not only addition it is seldom, and its Easily decompose at high temperature and generate free radicals and be consumed, and playing prevents in process raw material molecular weight to reduce, that is, prevents The effect that system viscosity reduces, therefore double 25 addition is not the reason for mixed system viscosity reduces yet.It is in conclusion mixed Closing system viscosity reduces and should be caused by the Specific Interactions between component, and the compatibility between this mixed system component is good Good, in compatible co-mixing system, the phenomenon that viscosity reduces after mixing is less, and also few documents and materials have related report.
Some performance parameters after polymer blending can be speculated with addition theoretical value, specifically true according to the following formula It is fixed (only consider key component herein, ignore content 2% and following component)：
P=c1P1+c2P2
P is addition theoretical values in formula, P1For the corresponding parametric values of component in mixture 1, c1For its mass fraction, P2For The corresponding parametric values of component 2, c in mixture2For its mass fraction.If the measured value of mixture parameter and the addition theoretical value phase Difference is bigger, and collaboration (or anti-collaboration) effect is more notable between showing component.
As can be found from Table 1, when shear rate is 100s-1When, actual blend apparent shear viscosity is than addition theoretical value Low about 48.3% (embodiment 1) is to 47.8% (embodiment 4).
As can be found from Table 2, when shear rate is 1363s-1When, actual blend apparent shear viscosity is than addition theoretical value Low about 44.8% (embodiment 1) is to 65.1% (embodiment 4).
【Embodiment 7】
7 kinds of particles of all of the above, including comparative example 1-2 and embodiment 1-5, as described above the step of carried out difference Show scanning calorimetric (DSC) test, temperature lowering curve and second of heating curve are shown in Fig. 6 and Fig. 7.Directly can therefrom it be obtained with software Each particle glass transition temperature (" Tg") with composition relation see Fig. 8.
As can be seen from Figure 6 the former crystallinity is decreased obviously after CAB is added in PHBV, the DSC drops of embodiment 1-5 Warm curve is hardly visible peak crystallization.On second of heating curve, except embodiment 1-2 has heating peak crystallization and melting peak Outside (wherein the crystallization of embodiment 2 and melting peak are smaller), embodiment 3-5 do not have substantially crystallization with melting signal.From Fig. 6-8 Understand that stuff and other stuff only has a glass transition temperature (" Tg"), it is fine to show to be blended the compatibility that respectively forms in particle, And TgNumerical value raised with the increase of CAB contents.
【Embodiment 8】
7 kinds of particles of all of the above, including comparative example 1-2 and embodiment 1-5, as described above the step of carried out heat Weight analysis (TGA) are tested, and test result is shown in Fig. 9.From the figure, it can be seen that the heat decomposition curve of particle is in comparative example after blending Between 1-2 curves, show that the heat endurance that front and rear CAB and PHBV is blended does not have too big change, this is consistent with expection. And two different stages are presented in the heat decomposition curve of blend, point with two of which primary raw material (PHBV and CAB) Solution temperature is corresponding, in addition, the ratios in two thermal decomposition stages are corresponding with the composition of blend.
【Embodiment 9】
7 kinds of particles of all of the above, including comparative example 1-2 and embodiment 1-5, as described above the step of melted Melt index (MFR) test (190 DEG C, 2.16kg), the relation between the MFR numerical value and composition that measure is shown in Figure 10.Obtained from Figure 10 Concrete numerical value be listed in table 3, including " addition theoretical value " mentioned above.
As can be found from Table 3, after each group lease making melt blending, the actual melt index of embodiment 1 is higher than addition theoretical value 16.8g/10min, percentage are about 89.4%, are that percent value is minimum in embodiment 1-5；The actual melting of embodiment 4 refers to Number is higher 39.7g/10min than addition theoretical value, and percentage is about 303%, is that percent value is maximum in embodiment 1-5.Remaining Embodiment is higher than addition theoretical value between 89.4%-303%.The extremely high melt index of the above is all unexpected , it is rare in the good polymer blends of compatibility, and in CAB and PHBV blends it is still undiscovered existing As.
【Embodiment 10】
7 kinds of particles by more than, including comparative example 1-2 and embodiment 1-5, the Thermo Fisher scientific ＆ technical corporation in the U.S. HAKKETMInjection experiment is carried out in MiniJet II miniature injection machines.Mould is the production of Thermo Fisher scientific ＆ technical corporation The pattern tool of 557-2295-60 × 10 × 1, expects that chamber temperature and mold temperature are set in experimentation：200 DEG C and 50 DEG C.Note Pressure is set to 300bar, time 5s during modeling, and follow-up pressure maintaining period keeps 60s for 100bar, demoulds afterwards, collects note Mould batten.
Under identical injecting condition, due to the difference of the mobile performance of material, it is molded performance also can be different, instead Reflect on the full level that injection obtains sample.All 7 kinds of injections battens are illustrated in fig. 11, and wherein starting material CAB is (right Ratio 2) prepare injection batten it is most short, illustrate under this condition, its mobility is minimum.It is prepared by starting material PBS (comparative example 1) Although injection batten it is more longer than comparative example 2, it is not still being full of mould.And by blending after, batten is substantially complete Portion is filled with mould, shows that being molded performance is significantly improved.Due to the raising of material flowing deformation performance after blending, in identical bar Under part, blend of the invention can prepare bigger, thinner moulding.High fluidity is additionally provided in same time at the same time Prepare the possibility of more injection-molded items.
In shear rate it is 100s at 1 180 DEG C of table-1When actual measurement apparent shear viscosity, theoretical apparent shear viscosity and Both differences and difference percentage
In shear rate it is 1363s at 2 180 DEG C of table-1When actual measurement apparent shear viscosity, theoretical apparent shear viscosity with And both differences and difference percentage
Table 3 surveys melt index (190 DEG C, 2.16kg) and addition theory melt index and both difference and difference hundred Fraction

Claims (10)

1. a kind of injection-molded item, thermoplastic cellulose and Microbe synthesis polyester blend containing graft modification, with mass fraction Meter, thermoplastic cellulose and the Microbe synthesis polyester blend of the graft modification include following components：
(1) 20 to 80 part of thermoplastic cellulose；
(2) 80 to 20 parts of Microbe synthesis polyester；
(3) 0.1 to 10 parts of reactive monomer；
It is characterized in that in the blend reactive monomer be at least grafted to thermoplastic cellulose and Microbe synthesis polyester its On one.
2. according to the injection-molded item described in claim 1, it is characterised in that the melt viscosity of the blend is in low sheraing speed Rate 100s-1Under the conditions of it is at least lower by about 50% than the blending addition theoretical value of two kinds of predominant starting materials, in high-rate of shear 1363s-1Under the conditions of it is at least lower by 45% than the blending addition theoretical value raw material of two kinds of predominant starting materials.
3. according to the injection-molded item described in claim 1, it is characterised in that the substitution value of the thermoplastic cellulose is more than 1.0；The further preferred thermoplastic cellulose is cellulose acetate-butyrate, acetic acid cellulose valerate ester, acetic acid caproic acid are fine The plain ester of dimension, acetic acid enanthic acid cellulose esters, laurate cellulose esters, acetic acid cellulose pelargonate ester, acetic acid capric acid cellulose esters, vinegar Sour laurate cellulose esters, acetic acid palmitic acid cellulose esters, acetic acid cellulose stearate ester, cellulose propionate butyrate ester, propionic acid Cellulose valerate ester, propionic acid cellulose caproate ester, propionic acid enanthic acid cellulose esters, propionic acid octanoic acid cellulose esters, propionic acid n-nonanoic acid fiber Plain ester, propionic acid capric acid cellulose esters, propionic acid laurate cellulose esters, propionic acid palmitic acid cellulose esters, propionic acid cellulose stearate At least one of ester.
4. according to the injection-molded item described in claim 1, it is characterised in that the Microbe synthesis polyester includes poly- 3- hydroxyls Base butyrate, poly- 3- hydroxyl valerates, poly- 3- hydroxycaproic esters, poly- 3- hydroxyheptanoates, poly- 3- Hydroxyoctanoic acids ester, poly- 3- hydroxyls Pelargonate, poly- 3- hydroxydecanoic acids ester, poly- 3- hydroxydecanoic acids ester, poly- 3- hydroxylaurics acid esters, poly- 3- hydroxyls palmitate, poly- 3- hydroxyls At least one of the polyhydroxyalkanoate such as base stearate.
5. according to the injection-molded item described in claim 1, it is characterised in that the Microbe synthesis polyester is included by two kinds Or the copolyesters that two or more hydroxy fatty acids are formed, it is preferably poly- 3-hydroxybutyrate -3- hydroxyl valerates, poly- 3- hydroxyls fourth Sour -4 butyric esters, poly- 3-hydroxybutyrate -3- hydroxycaproic esters, poly- 3-hydroxybutyrate -3- hydroxyheptanoates, poly- 3- hydroxyls fourth Acid -3- Hydroxyoctanoic acid esters, poly- 3-hydroxybutyrate -3- hydroxynonanoates, poly- 3-hydroxybutyrate -3- hydroxydecanoic acid esters, poly- 3- hydroxyls Butyric acid -3- hydroxylauric acid esters, poly- 3-hydroxybutyrate -3- hydroxyl palmitates, poly- 3-hydroxybutyrate -3- hydroxy stearic acid esters； Poly- 3- hydroxypentanoic acids -3- hydroxycaproic esters, poly- 3- hydroxypentanoic acids -3- hydroxyheptanoates, poly- 3- hydroxypentanoic acids -3- Hydroxyoctanoic acids Ester, poly- 3- hydroxypentanoic acids -3- hydroxynonanoates, poly- 3- hydroxypentanoic acids -3- hydroxydecanoic acid esters, the poly- 3- hydroxypentanoic acids -3- hydroxyl moons Cinnamic acid ester, poly- 3- hydroxypentanoic acids -3- hydroxyl palmitates, poly- 3- hydroxypentanoic acids -3- hydroxy stearic acid esters；Poly- 3- hydroxycaproic acids- 3- hydroxyheptanoates, poly- 3- hydroxycaproic acids -3- Hydroxyoctanoic acid esters, poly- 3- hydroxycaproic acids -3- hydroxynonanoates, poly- 3- hydroxyls oneself Acid -3- hydroxydecanoic acid esters, poly- 3- hydroxycaproic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxycaproic acids -3- hydroxylauric acid esters, poly- 3- hydroxyls Base caproic acid -3- hydroxyl palmitates, poly- 3- hydroxycaproic acids -3- hydroxy stearic acid esters；Poly- 3- hydroxyheptanoic acids -3- Hydroxyoctanoic acid esters, Poly- 3- hydroxyheptanoic acids -3- hydroxynonanoates, poly- 3- hydroxyheptanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxyheptanoic acids -3- hydroxylauric acids Ester, poly- 3- hydroxyheptanoic acids -3- hydroxyl palmitates, 3- hydroxyheptanoic acid -3- hydroxy stearic acid esters；Poly- 3- Hydroxyoctanoic acids -3- hydroxyls Pelargonate, poly- 3- Hydroxyoctanoic acids -3- hydroxydecanoic acid esters, poly- 3- Hydroxyoctanoic acids -3- hydroxydecanoic acid esters, poly- 3- Hydroxyoctanoic acids -3- hydroxyls Base laurate, poly- 3- Hydroxyoctanoic acids -3- hydroxyl palmitates, poly- 3- Hydroxyoctanoic acids -3- hydroxy stearic acid esters；Poly- 3- hydroxyls nonyl Acid -3- hydroxydecanoic acid esters, poly- 3- hydroxynonanoic acids -3- hydroxydecanoic acid esters, poly- 3- hydroxynonanoic acids -3- hydroxylauric acid esters, poly- 3- hydroxyls Base n-nonanoic acid -3- hydroxyl palmitates, poly- 3- hydroxynonanoic acids -3- hydroxy stearic acid esters；Poly- 3- hydroxydecanoic acids -3- hydroxylauric acids At least one of ester, poly- 3- hydroxydecanoic acids -3- hydroxyl palmitates, poly- 3- hydroxydecanoic acids -3- hydroxy stearic acid esters etc..
6. according to the injection-molded item described in claim 1, it is characterised in that the reactive monomer preferably with hydroxyl, Carboxyl, carbonyl, ester group, amino, sulfydryl, sulfonic group, ehter bond, halogen, peptide bond, anhydride bond polar group and also contain unsaturated carbon At least one of compound of carbon double bond；More preferably maleic acid anhydride, acrylic compounds, methacrylic, propylene At least one of esters of gallic acid, methyl acrylic ester, acrylic amide, methacryl amine compound；More preferably third At least one of olefin(e) acid esters and methyl acrylic ester compound, are most preferably acrylic acid hydroxy alkyl ester and methacrylic acid At least one of hydroxy alkyl ester.
7. according to the injection-molded item described in claim 1, it is characterised in that the blend further includes：(4) 0.01 to 1 parts Initiator.
8. according to the injection-molded item described in claim 7, it is characterised in that the initiator is radical initiator；It is preferred that For：In acyl peroxide, alkyl peroxide, perester, alkyl peroxide, ketone peroxide, azo compound extremely Few one kind；More preferably：Benzoyl peroxide, azo-bis-isobutyl cyanide, cumyl peroxide, di-t-butyl peroxide, At least one of tert-butyl hydroperoxide, perbenzoic acid, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes；It is more excellent Elect as：At least one of benzoyl peroxide, 2,5- dimethyl -2,5- di-t-butyl hexane peroxides.
A kind of 9. method for preparing any injection-molded item of claim 1~8, by the desired amount of each group lease making mixing granulation Afterwards, it is injected on injection molding machine after fusion plastification by injection screw in mold cavity and forms blend melt, the blending Thing melt is through pressurize in mold cavity, and after cooling, departing from injection mold becomes the injection-molded item.
10. a kind of method for preparing any injection-molded item of claim 1~8, is added to core material or blend It is injected on extra quality common injection molding machine after fusion plastification by injection screw in mold cavity, departs from note after pressurize and cooling Mould becomes the core layer of injection-molded item, and skin-material or blend are added on another injection molding machine and equipped with core Injection, pressurize and it is cooled into preparing double injection product behind top layer in another mold cavity of layer；Wherein, the bilayer At least one layer of thermoplastic cellulose for graft modification of injection-molded item and Microbe synthesis polyester blend, are all grafting when two layers When modified thermoplastic cellulose is with Microbe synthesis polyester blend, the thermoplastic cellulose of the graft modification in two layers with it is micro- Biosynthesis polyester blend has thermoplastic cellulose, Microbe synthesis polyester, the reactive monomer of different proportion of composing And initiator.
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