CN106832530A - A kind of degradable biological synthetic resin and preparation method thereof - Google Patents
A kind of degradable biological synthetic resin and preparation method thereof Download PDFInfo
- Publication number
- CN106832530A CN106832530A CN201710130388.0A CN201710130388A CN106832530A CN 106832530 A CN106832530 A CN 106832530A CN 201710130388 A CN201710130388 A CN 201710130388A CN 106832530 A CN106832530 A CN 106832530A
- Authority
- CN
- China
- Prior art keywords
- preparation
- synthetic resin
- biomass
- degradable biological
- mixing device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention provides a kind of degradable biological synthetic resin, by by mass fraction for 30 70% resin, mass fraction is 0.5 10% compatilizer, mass fraction is 0.5 3% lubricant, biomass and inorganic filler, by blending, obtained after extrusion, beneficial effect with prior art is, diisocyanate and isocyanates with high reaction activity are incorporated into compatilizer system, moisture present in biomass is made full use of to participate in the polymerisation of isocyanates, dry effect is played while chemical bonding is set up, and discharge of the generation carbon dioxide in technical process, it is prevented effectively from the reunion of biomass and hardened, the height of resin material is conducive to sneak out journey；Increase the cooperative effect between compatilizer, help to form appropriate cross-linked structure in biological surface, introduce active double bond, realize the strong bonded of C C keys between biological surface and resin matrix, increase the mechanical performance of material.
Description
Technical field
The present invention relates to biosynthesis resin technology field, specially a kind of degradable biological synthetic resin and its preparation side
Method.
Background technology
Biosynthesis resin is using the micro mist of agricultural by-products as biomass filler, using resins for universal use as the one of matrix
Plant Novel environment-friendlymaterial material.The production of biosynthesis resin can preferably utilize agricultural by-products, reduce the useless of agricultural by-products
Abandon and burn, consumption of the naval stores to petroleum resources can be reduced, therefore with great Significance for Environment and practical value.
One feature of biosynthesis resin is exactly with preferable degradable ability.It is biological in biosynthesis resin
The content of matter accounts for overall 30%~50%, and biomass portion with degradable, and can turn into during degraded
The nutrient source of microbial growth, therefore biosynthesis resin is relative to potting resin high and ordinary resin, from internal composition just
Advantage with degraded.
Existing biosynthesis resin compatible agent, mainly by foundationization between the hydroxyl and compatilizer of biological surface
Learn bonding, the reaction of such as reaction of hydroxyl and maleic anhydride and its derivative, or hydroxyl and silane coupler, also or other work
Reaction of the property between group and epoxy radicals, hydroxyl or carboxyl.The reactivity of these chemical reactions hence sets up generally than relatively low
The efficiency comparison of the chemical bonds between biomass and compatilizer, or even resin matrix is poor, thus have impact on the mechanical property of materials
Stability.
The content of the invention
To solve above-mentioned technological deficiency, the technical solution adopted by the present invention is, there is provided a kind of degradable biological synthesis tree
The preparation method of fat, it is characterised in that it is comprised the following steps：
The first step：By mass fraction for the biomass of 20-60% are added to the modeling with height air-tightness and antiseptic power
In expecting mixing device high, and it is 70 DEG C to maintain the temperature of mixing device high；
Second step：It is the compatilizer A of 0.01-0.5% to addition mass fraction in mixing device high, after mixing 5min, and will
The temperature of mixing device high is increased to 95-100 DEG C, continues to knead 5min；
3rd step：It is the compatilizer B of 0.49-9.5% to continue to mass fraction is added in mixing device high, kneads 10min, together
When be naturally cooling to 80 DEG C；
4th step：It is 5-30%'s for the resin of 30-70%, mass fraction that mass fraction is added in most backward mixing device high
Inorganic filler and mass fraction are the lubricant of 0.5-3%, while the temperature of mixing device high is increased into 85 DEG C, knead 20min-
30min, cools down after discharging, obtains biomass/resin premixed material；
5th step：By the premix described in the 4th step by after extrusion, granulation, obtaining biomass/masterbatch resin product.
Preferably, the compatilizer A includes one or more in isocyanates, diisocyanate.
Preferably, the isocyanates is allyl iso cyanurate.
Preferably, the diisocyanate includes 1,6- hexylidene diisocyanates, methyl diphenylene diisocyanate, first
One or more in phenylene diisocyanate.
Preferably, the compatilizer B includes epoxidized vegetable oil, OPE, the polyethylene of oxidation modification, polyethylene
Alcohol, maleic anhydride, maleic anhydride derivative, ethylene/vinyl alcohol block copolymer, ethylene/vinyl acetate copolymer, ethylene/propylene
One or more in olefin(e) acid ester copolymer, the polyolefin of maleic anhydride grafting/copolymerization, silane coupler, glycerine.
Preferably, the resin is resins for universal use.
Preferably, described lubricant include Tissuemat E, change surname Tissuemat E, silicone oil, fluoroelastomer, boron nitride,
One or more in stearate, palmitate, laurate.
Preferably, the biomass include that rice husk, stalk, corncob, the micro mist of dregs of beans, coffee shell micro mist, coconut skin are micro-
One or more in powder.
Preferably, the particle diameter of the biomass micro mist is 5-120 μm.
Preferably, a kind of degradable biological synthetic resin.
Compared with prior art, the present invention provides a kind of degradable biological synthetic resin and preparation method thereof, will be with high
The diisocyanate and isocyanates of reactivity are incorporated into compatilizer system, are had the advantages that：
1st, the polymerisation of isocyanates is sufficiently participated in using moisture present in biomass, chemical bonding is being set up
Dry effect is played simultaneously, while the re-absorption of moisture can also be avoided, so as to reach more preferable resultant effect；
2nd, NCO and hydrone react, and generate amine and carbon dioxide, and carbon dioxide is in technical process
Discharge can effectively avoid the reunion of biomass and hardened, be conducive to the height of resin material to sneak out journey；
3rd, increase the cooperative effect between compatilizer, help to form appropriate cross-linked structure in biological surface, introduce
Active double bond, so as to more easily realize the strong bonded of C-C keys between biological surface and resin matrix, increases material
Mechanical performance.
4th, can be more efficient on biological surface formed flexible robust organic coating layer, closing biomass it is porous
Surface, while the sustained release of small organic molecule can be reduced.
5th, synergy can be produced with silane coupler, and then reaches more preferable surface treatment effect.
6th, can and biomass form good combination, offset after lubricant stearic acid salt use compatilizer to imitate so as to overcome
The negative effect of fruit, it is ensured that biosynthesis resin system has good combination property.
Brief description of the drawings
In order to illustrate more clearly of the technical scheme in various embodiments of the present invention, below will be to being wanted needed for embodiment description
The accompanying drawing for using is briefly described.
Fig. 1 is the photo of surface treated dregs of beans, stalk, Mai Pi and rice husk sample in the present invention；
Fig. 2 is the stereoscan photograph of surface treated dregs of beans, stalk, Mai Pi and rice husk sample in the present invention；
Fig. 3 is the adsorption/desorption curve of surface treated fibrous straw powder in the present invention；
Fig. 4 is the adsorption/desorption curve of surface treated rice chaff powder in the present invention；
Specific embodiment
Below in conjunction with accompanying drawing, the technical characteristic above-mentioned and other to the present invention and advantage are described in more detail.
Embodiment 1
Dregs of beans micro mist by 100 parts of particle diameter D97 values for 35 μm is added to the plastics with height air-tightness and antiseptic power
In mixing device high, and the temperature of mixing device high is maintained for 70 DEG C, to being added in mixing device high, 2 parts of atoleines and 1 part of 1,6- are sub-
Hexyl diisocyanate, after mixing 5min, 95-100 DEG C is increased to by the temperature of mixing device high, continues to knead 5min.It is mixed in height
3 parts of epoxidized soybean oil, 1 part of silane coupler is added to knead 10min in equipment, while after being naturally cooling to 80 DEG C, being set to height is mixed
Standby middle addition melting range is 90 °C -110 DEG C of 5 parts of paraffin (PE waxes), and 100 parts of PE resin particles material, particle diameter is the calcium carbonate of 200 mesh
20 parts, particle diameter is 5 parts of the calcium carbonate of 1800 mesh, 3 parts of zinc stearate.The temperature of mixing device high is increased to 85 DEG C, mixing
20min, cools down after discharging, obtains the biomass/resin premixed material of and cladding treatment modified by surface.
Embodiment 2
The present embodiment is that the zinc stearate use equally has the poly- second of lubrication with the difference of embodiment 1
Alkene wax and change surname Tissuemat E mixture replace, the silane coupler OPE, the polyethylene of oxidation modification,
A kind of replacement in polyvinyl alcohol and glycerine.
Embodiment 3
The present embodiment is that the zinc stearate uses the same palm with lubrication with the difference of embodiment 1
Sour zinc and lauric mixture replace, silane coupler ethylene/vinyl alcohol block copolymer, ethylene/vinyl acetate
The mixture of copolymer and ethene/acrylic ester copolymer replaces.
Embodiment 4
The present embodiment is with the difference of embodiment 1, the zinc stearate with the same silicone oil with lubrication,
Fluoroelastomer and boron nitride replace, the silane coupler maleic anhydride, maleic anhydride derivative, maleic anhydride grafting/
The mixture of the polyolefin of copolymerization replaces.
Embodiment 5
The present embodiment is that the dregs of beans micro mist is replaced by stalk, the D97 of the stalk with the difference of embodiment 1
Be worth is 40 μm.
Embodiment 6
The present embodiment is that the dregs of beans micro mist is replaced by wheat skin with the difference of embodiment 1, the D97 of the wheat skin
Be worth is 45 μm.
Embodiment 7
The present embodiment is that the dregs of beans micro mist is replaced by powdered rice hulls, the powdered rice hulls with the difference of embodiment 1
D97 values are 48 μm.
Embodiment 8
The present embodiment is that the dregs of beans micro mist is by coffee shell micro mist and coconut skin micro mist with the difference of embodiment 1
Instead of the D97 values of the coffee shell micro mist are 80 μm, and the D97 values of the coconut skin micro mist are 100 μm.
Embodiment 9
The present embodiment is that 1, the 6- hexylidene diisocyanates are by pi-allyl isocyanide with the difference of embodiment 1
Acid esters replaces, and finally gives the biomass/tree of and cladding treatment on biological surface introducing activated double bonds modified by surface
Fat premix.
Embodiment 10
The present embodiment is that the dregs of beans micro mist is by stalk, wheat skin, powdered rice hulls, coffee shell with the difference of embodiment 9
One or more replacements in micro mist and coconut skin micro mist, and the D97 values of the stalk are 40 μm, the D97 values of the wheat skin are
45 μm, the D97 values of the powdered rice hulls are 48 μm, and the D97 values of the coffee shell micro mist are 80 μm, the D97 of the coconut skin micro mist
Be worth is 100 μm.
Embodiment 11
The present embodiment is that 1, the 6- hexylidene diisocyanates are by diisocyanate with the difference of embodiment 1
Replace with isocyanate mixture, and the diisocyanate and isocyanate mixture are 1,6- hexylidene diisocyanates,
Methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), the mixture of allyl iso cyanurate, finally give and change by surface
Property and cladding treatment on biological surface introduce activated double bonds biomass/resin premixed material.
Embodiment 12
The present embodiment is that the dregs of beans micro mist is by stalk, wheat skin, powdered rice hulls, coffee with the difference of embodiment 11
A kind of replacement in shell micro mist and coconut skin micro mist, and the D97 values of the stalk are 40 μm, the D97 values of the wheat skin are 45 μm,
The D97 values of the powdered rice hulls are 48 μm.
Refer to shown in Fig. 1, Fig. 2, Fig. 3 and Fig. 4,
Fig. 1 is the photo of surface treated dregs of beans, stalk, Mai Pi and rice husk sample；
Fig. 2 is the stereoscan photograph of surface treated dregs of beans, stalk, Mai Pi and rice husk sample；
Fig. 3 is the adsorption/desorption curve of surface treated fibrous straw powder；
Fig. 4 is the adsorption/desorption curve of surface treated rice chaff powder.
Dregs of beans, stalk, Mai Pi and rice after photo and stereoscan photograph (such as Fig. 1 and Fig. 2) observe surface treatment
The apparent and microscopic appearance of shell sample, it can be seen that by after surface treatment, showing for serious caking does not occur in biomass powder
As.And according to adsorption/desorption curve (such as Fig. 3 and Fig. 4) as can be seen that after surface treatment, rice chaff powder and maize straw powder
There is not the pore structure of complexity.This is, because NCO reacts with hydrone, to generate amine and carbon dioxide, dioxy
Changing discharge of the carbon in technical process can effectively avoid the reunion of biomass and hardened, be conducive to the height of resin material to sneak out
Journey.
Embodiment 13
By 3 parts of the paraffin (PE waxes) that melting range is 90 DEG C~110 DEG C, 100 parts of LDPE resin particulate material, LLDPE resins are added
20 parts of particulate material, 30 parts of HDPE resin particle, particle diameter is 10 parts of the calcium carbonate of 500 mesh, and particle diameter is 5 parts of the calcium carbonate of 1800 mesh,
2 parts of calcium stearate is added to temperature and is 70 DEG C has a plastic high-speed mixer equipment of antiseptic power, and by the temperature liter of mixing device high
Height kneads 20min to 85 DEG C, is cooled down after discharging, obtains resin premixed material.
Premix of the height after mixed is cooled down into mixing in cold mixer, and extrusion unit is added to by multi screw stem material feeding machine
In, specific procession parameters such as following table.
Table 1
Meanwhile, in order to avoid the suction of moisture in cooling procedure, cause the performance loss of product, using die face earnestly and wind
The synthetic resin of blending/reactive extrursion is manufactured into masterbatch resin product by the technique of cold drawn bar pelletizing, finally, the conjunction that will be prepared
Resin particle is made film product.
Embodiment 14
The present embodiment and the preparation that the difference part of embodiment 13 is premix, it is specific as follows：
By 30 parts of particle diameter D97 values for 48 μm of rice chaff micro mists are added in the plastic high-speed mixer equipment with antiseptic power, maintain
The temperature of mixing device high is 70 DEG C, to 3 parts of the paraffin (PE waxes) that melting range is 90 DEG C~110 DEG C is added in mixing device high, is added
100 parts of LDPE resin particulate material, 20 parts of LLDPE resin particles material, 30 parts of HDPE resin particle, particle diameter is the calcium carbonate of 500 mesh
10 parts, particle diameter is 5 parts of the calcium carbonate of 1800 mesh, 2 parts of calcium stearate.The temperature of mixing device high is increased to 85 DEG C, mixing
20min, cools down after discharging, obtains the biomass/resin premixed material processed by Surface coating.
Embodiment 15
The present embodiment and the preparation that the difference part of embodiment 13 is premix, it is specific as follows：
By 30 parts of particle diameter D97 values for 48 μm of rice chaff micro mists are added in the plastic high-speed mixer equipment with antiseptic power, maintain
The temperature of mixing device high is 70 DEG C, to 3 parts of epoxidized soybean oil is added in mixing device high, after mixing 10min, is added in mixing device high
Enter 3 parts of the paraffin (PE waxes) that melting range is 90 DEG C~110 DEG C, add 100 parts of LDPE resin particulate material, LLDPE resin particles material 20
Part, 30 parts of HDPE resin particle, particle diameter is 10 parts of the calcium carbonate of 500 mesh, and particle diameter is 5 parts of the calcium carbonate of 1800 mesh, calcium stearate 2
Part.The temperature of mixing device high is increased to 85 DEG C, 20min is kneaded, cooled down after discharging, obtain the biology processed by Surface coating
Matter/resin premixed material.
Embodiment 16
The present embodiment and the preparation that the difference part of embodiment 13 is premix, it is specific as follows：
By 30 parts of particle diameter D97 values for 48 μm of rice chaff micro mists are added to the plastic high-speed mixer with height air-tightness and antiseptic power
In equipment, the temperature for maintaining mixing device high is 70 DEG C, to addition 1 part of atoleine and 1 part of 1,6- hexylidene two in mixing device high
Isocyanates, after mixing 5min, 95~100 DEG C is increased to by the temperature of mixing device high, adds 0.5 part of maleic anhydride, continues mixed
Refining 5min.2 parts of epoxidized soybean oil, 0.5 part of silane coupler is added 10min to be kneaded, while being naturally cooling in mixing device high
After 80 DEG C, to 3 parts of the paraffin (PE waxes) that melting range is 90 DEG C~110 DEG C is added in mixing device high, LDPE resin particulate material 100 is added
Part, 20 parts of LLDPE resin particles material, 30 parts of HDPE resin particle, particle diameter is 10 parts of the calcium carbonate of 500 mesh, and particle diameter is 1800 mesh
5 parts of calcium carbonate, 2 parts of calcium stearate.The temperature of mixing device high is increased to 85 °C, 20min is kneaded, cooled down after discharging, obtained
Biomass/resin premixed the material of modified and cladding treatment by surface.
Embodiment 17
The present embodiment be with the difference of embodiment 16 added in the present embodiment 1 part of silane coupler, 0.3 part
Maleic anhydride and 0.2 part of allyl iso cyanurate, meanwhile, it is also added into 1 part of PE- copolymer-maleic anhydride and the micro tert-butyl group
Peroxide.
Embodiment 18
The present embodiment be with the difference of embodiment 16 added in the present embodiment 1 part of silane coupler, 0.2 part
Maleic anhydride and 0.1 part of allyl iso cyanurate, meanwhile, it is also added into 1 part of PE- copolymer-maleic anhydride.
Embodiment 19
The present embodiment is by institute in embodiment 13, embodiment 14, embodiment 15, embodiment 16, embodiment 17 and embodiment 18
Obtained biosynthesis resin film product, carries out tensile property test, obtains data as shown in table 2.
Table 2
| Numbering | Tensile strength | Elongation at break | Detection method | Tensile elongation | Draw speed |
| Embodiment 13 | 28.82MPa | 1170.84% | ASTMD882 | 50mm | 500mm/min |
| Embodiment 14 | 17.60MPa | 756.67% | ASTMD882 | 50mm | 500mm/min |
| Embodiment 15 | 17.98MPa | 631.50% | ASTMD882 | 50mm | 500mm/min |
| Embodiment 16 | 32.04MPa | 411.12% | ASTMD882 | 50mm | 500mm/min |
| Embodiment 17 | 23.24MPa | 747.95% | ASTMD882 | 50mm | 500mm/min |
| Embodiment 18 | 26.07MPa | 1185.17% | ASTMD882 | 50mm | 500mm/min |
The surface treatment by compatilizer and isocyanates, the machine of biosynthesis resin are can be seen that from the data in table 2
Tool performance is greatly improved than being added without the resin of auxiliary agent in embodiment 14, does not add the pure tree of biomass with embodiment 13 substantially
Fat prod is suitable, with good mechanical property.This is due to the isocyanates with high reaction activity is incorporated into compatilizer
In system, the cooperative effect between compatilizer is increased, help to form appropriate cross-linked structure in biological surface, introduced and live
Bold and vigorous double bond, so as to more easily realize the strong bonded of C-C keys between biological surface and resin matrix, and then increased material
The mechanical performance of material.
Embodiment 20
By 30 parts of particle diameter D97 values for 48 μm of rice chaff micro mists are added to the plastic high-speed mixer with height air-tightness and antiseptic power
In equipment, the temperature for maintaining mixing device high is 70 DEG C, to addition 1 part of atoleine and 1 part of 1,6- hexylidene two in mixing device high
Isocyanates, after mixing 5min, 95~100 DEG C is increased to by the temperature of mixing device high, adds 0.5 part of maleic anhydride, continues mixed
Refining 5min.2 parts of epoxidized soybean oil, 0.5 part of silane coupler is added 10min to be kneaded, while being naturally cooling in mixing device high
After 80 DEG C, to 3 parts of the paraffin that melting range is 90 DEG C~110 DEG C is added in mixing device high, 150 parts of acrylic resin particulate material is added,
Particle diameter is 10 parts of the calcium carbonate of 500 mesh, and particle diameter is 5 parts of the calcium carbonate of 1800 mesh, 2 parts of calcium stearate.By the temperature of mixing device high
It is increased to 85 DEG C, kneads 20min, cooled down after discharging, obtains the biomass of and cladding treatment modified by surface/resin premixed
Material.
Premix of the height after mixed is cooled down into mixing in cold mixer, and extrusion unit is added to by multi screw stem material feeding machine
In, specific procession parameters such as table 3.
Table 3
Meanwhile, in order to avoid the suction of moisture in cooling procedure, cause the performance loss of product, using die face earnestly and wind
The synthetic resin of blending/reactive extrursion is manufactured into masterbatch resin product by the technique of cold drawn bar pelletizing, finally, the conjunction that will be prepared
Resin particle is made film product.
Embodiment 21
The present embodiment is that the acrylic resin particulate material is by Corvic with the difference part of embodiment 19
Pellet replaces, and the specific procession parameters such as table 4.
Table 4
Embodiment 22
The present embodiment is that the polyvinyl chloride resin particle material is by ABS resin particle with the difference part of embodiment 19
Material replaces, and the specific procession parameters such as table 5.
Table 5
Claims (10)
1. a kind of preparation method of degradable biological synthetic resin, it is characterised in that it is comprised the following steps：
The first step：Mass fraction is high for the biomass of 20-60% are added to the plastics with height air-tightness and antiseptic power
In mixing device, and maintain mixing device high temperature be 70 DEG C；
Second step：It is after mixing 5min and height is mixed to adding mass fraction to be the compatilizer A of 0.01-0.5% in mixing device high
The temperature of equipment is increased to 95-100 DEG C, continues to knead 5min；
3rd step：It is the compatilizer B of 0.49-9.5% to continue to mass fraction is added in mixing device high, kneads 10min, while from
So it is cooled to 80 DEG C；
4th step：Addition mass fraction is the resin of 30-70%, mass fraction for 5-30%'s is inorganic in most backward mixing device high
Filler and mass fraction are the lubricant of 0.5-3%, while the temperature of mixing device high is increased into 85 DEG C, knead 20min-
30min, cools down after discharging, obtains biomass/resin premixed material；
5th step：By the premix described in the 4th step by after extrusion, granulation, obtaining biomass/masterbatch resin product.
2. the preparation method of degradable biological synthetic resin according to claim 1, it is characterised in that the compatilizer A
Including one or more in isocyanates, diisocyanate.
3. the preparation method of degradable biological synthetic resin according to claim 2, it is characterised in that the isocyanates
It is allyl iso cyanurate.
4. the preparation method of degradable biological synthetic resin according to claim 2, it is characterised in that two isocyanic acid
Ester includes one or more in 1,6- hexylidene diisocyanates, methyl diphenylene diisocyanate, toluene di-isocyanate(TDI).
5. the preparation method of degradable biological synthetic resin according to claim 1, it is characterised in that the compatilizer B
Derive including epoxidized vegetable oil, OPE, the polyethylene of oxidation modification, polyvinyl alcohol, maleic anhydride, maleic anhydride
Thing, ethylene/vinyl alcohol block copolymer, ethylene/vinyl acetate copolymer, ethene/acrylic ester copolymer, maleic anhydride connect
One or more in polyolefin, silane coupler, the glycerine of branch/copolymerization.
6. degradable biological synthetic resin according to claim 1 and preparation method thereof, it is characterised in that the resin is
Resins for universal use.
7. the preparation method of degradable biological synthetic resin according to claim 1, it is characterised in that described lubricant
Including Tissuemat E, change surname Tissuemat E, silicone oil, fluoroelastomer, boron nitride, stearate, palmitate, laurate
One or more.
8. the preparation method of degradable biological synthetic resin according to claim 1, it is characterised in that the biomass bag
Include one or more in rice husk, stalk, corncob, the micro mist of dregs of beans, coffee shell micro mist, coconut skin micro mist.
9. the preparation method of degradable biological synthetic resin according to claim 8, it is characterised in that the biomass are micro-
The particle diameter of powder is 5-120 μm.
10. the degradable biological for being prepared with the preparation method of the degradable biological synthetic resin described in the claim 1-9 is closed
Resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710130388.0A CN106832530A (en) | 2017-03-07 | 2017-03-07 | A kind of degradable biological synthetic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710130388.0A CN106832530A (en) | 2017-03-07 | 2017-03-07 | A kind of degradable biological synthetic resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106832530A true CN106832530A (en) | 2017-06-13 |
Family
ID=59138951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710130388.0A Pending CN106832530A (en) | 2017-03-07 | 2017-03-07 | A kind of degradable biological synthetic resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106832530A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276762A (en) * | 2018-01-05 | 2018-07-13 | 武汉理工大学 | A kind of compound polyurethane material and preparation method for water lubriucated bearing |
| CN110951274A (en) * | 2019-12-24 | 2020-04-03 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material using sugarcane biomass powder as raw material |
| CN110964339A (en) * | 2019-12-24 | 2020-04-07 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material film with good air tightness |
| CN111019251A (en) * | 2019-12-24 | 2020-04-17 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of inorganic nanoparticle-doped bio-based composite material |
| DE102020121552B4 (en) | 2019-12-24 | 2023-01-19 | Liaoning Xingfuren Technology Co., Ltd. | PROCESS FOR MANUFACTURING BIO-BASED COMPOSITES USING PALM BIOMASS POWDER AS RAW MATERIAL |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315471A (en) * | 2000-03-31 | 2001-10-03 | 王友桐 | Plant fiber composite material, product thereof and manufacturing method thereof |
| CN1948399A (en) * | 2005-10-11 | 2007-04-18 | 中国林业科学研究院木材工业研究所 | Isocyanate strengthened agricultural residue fiber/plastic composite material and its preparation method |
| CN101392099A (en) * | 2008-10-23 | 2009-03-25 | 福建师范大学 | Method for preparing Wood-plastic composite material by modified wood powder and waste and old plastics |
| CN101875790A (en) * | 2010-08-09 | 2010-11-03 | 东北林业大学 | Surface hydrolysis modified aramid fiber enhanced wood plastic composite material and preparation method thereof |
| CN102051002A (en) * | 2010-12-02 | 2011-05-11 | 东北林业大学 | Zymolytic lignin-wood fiber-polyolefin hybrid composite material and preparation method thereof |
| CN102321374A (en) * | 2011-07-29 | 2012-01-18 | 东北林业大学 | Fire-retardant polyolefin based wood plastic composite material and preparation method thereof |
| CN102417740A (en) * | 2011-10-08 | 2012-04-18 | 福建师范大学 | Surface modification method for reinforcing interface compatibility of plant fibre/polymer based composite through two steps |
| CN103435818A (en) * | 2013-08-31 | 2013-12-11 | 东营泰然材料科技股份有限公司 | Method for carrying out hydrophobic modification on wood meal through mono-isocyanate and application method thereof |
| CN104761818A (en) * | 2015-04-25 | 2015-07-08 | 桂林理工大学 | Method for preparing polypropylene-based wood-plastic composite material by using straw |
| CN105419372A (en) * | 2015-12-27 | 2016-03-23 | 泉州市奈斯材料科技有限公司 | Method of preparing wood-plastic composite material with modified wood powder and waste plastic |
-
2017
- 2017-03-07 CN CN201710130388.0A patent/CN106832530A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315471A (en) * | 2000-03-31 | 2001-10-03 | 王友桐 | Plant fiber composite material, product thereof and manufacturing method thereof |
| CN1948399A (en) * | 2005-10-11 | 2007-04-18 | 中国林业科学研究院木材工业研究所 | Isocyanate strengthened agricultural residue fiber/plastic composite material and its preparation method |
| CN101392099A (en) * | 2008-10-23 | 2009-03-25 | 福建师范大学 | Method for preparing Wood-plastic composite material by modified wood powder and waste and old plastics |
| CN101875790A (en) * | 2010-08-09 | 2010-11-03 | 东北林业大学 | Surface hydrolysis modified aramid fiber enhanced wood plastic composite material and preparation method thereof |
| CN102051002A (en) * | 2010-12-02 | 2011-05-11 | 东北林业大学 | Zymolytic lignin-wood fiber-polyolefin hybrid composite material and preparation method thereof |
| CN102321374A (en) * | 2011-07-29 | 2012-01-18 | 东北林业大学 | Fire-retardant polyolefin based wood plastic composite material and preparation method thereof |
| CN102417740A (en) * | 2011-10-08 | 2012-04-18 | 福建师范大学 | Surface modification method for reinforcing interface compatibility of plant fibre/polymer based composite through two steps |
| CN103435818A (en) * | 2013-08-31 | 2013-12-11 | 东营泰然材料科技股份有限公司 | Method for carrying out hydrophobic modification on wood meal through mono-isocyanate and application method thereof |
| CN104761818A (en) * | 2015-04-25 | 2015-07-08 | 桂林理工大学 | Method for preparing polypropylene-based wood-plastic composite material by using straw |
| CN105419372A (en) * | 2015-12-27 | 2016-03-23 | 泉州市奈斯材料科技有限公司 | Method of preparing wood-plastic composite material with modified wood powder and waste plastic |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276762A (en) * | 2018-01-05 | 2018-07-13 | 武汉理工大学 | A kind of compound polyurethane material and preparation method for water lubriucated bearing |
| CN110951274A (en) * | 2019-12-24 | 2020-04-03 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material using sugarcane biomass powder as raw material |
| CN110964339A (en) * | 2019-12-24 | 2020-04-07 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material film with good air tightness |
| CN111019251A (en) * | 2019-12-24 | 2020-04-17 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of inorganic nanoparticle-doped bio-based composite material |
| CN110964339B (en) * | 2019-12-24 | 2022-03-29 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material film with good air tightness |
| DE102020121552B4 (en) | 2019-12-24 | 2023-01-19 | Liaoning Xingfuren Technology Co., Ltd. | PROCESS FOR MANUFACTURING BIO-BASED COMPOSITES USING PALM BIOMASS POWDER AS RAW MATERIAL |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832530A (en) | A kind of degradable biological synthetic resin and preparation method thereof | |
| CN1058736C (en) | Preparing method for biodegradation compound and its use | |
| WO2008136314A9 (en) | Polymer composite material, apparatus for producing the same and method of producing the same | |
| CN102311630B (en) | Fully biodegradable aliphatic polycarbonate mulch film and preparation method thereof | |
| CN101993558A (en) | Thin film produced by using starch fiber waste plastic | |
| CN103131070B (en) | Low-permeability and high-strength film and preparation method of the same | |
| US11814500B2 (en) | Algae-blended thermoplastic compositions | |
| CN1530399A (en) | Polyamide and polyolefine blend containing nanometer filler and with polyamide as matrix | |
| CN1575186A (en) | Hard capsules based on polysaccharide and method for the production thereof | |
| CN112048167A (en) | Degradable thermoplastic elastomer and preparation method thereof | |
| CN106432814B (en) | A kind of starch/polyethylene alcohol composite material and preparation method | |
| CN1876699A (en) | Microwave radioradiation crosslinked complete biodegradable material and its processing method | |
| CN104987540A (en) | Biomass-based thermoplastic elastic master batch and preparation method thereof | |
| CN109627629A (en) | A kind of self-cleaning antibacterial wood plastic composite and preparation method thereof | |
| CN101792609B (en) | Formula and preparation method of polyethylene based wood-plastic composite material | |
| KR102226172B1 (en) | Packaging container for fermented food and method of manufacturing thereof | |
| CN106905583A (en) | A kind of use agricultural by-products are close degradable synthetic resin of ambient time regulation type of raw material and preparation method thereof | |
| CN113698674A (en) | Biodegradable high-performance particle material with ceramic texture and preparation method thereof | |
| KR20170084588A (en) | A foamed plastic composition comprising biomass and a method of manufacturing thereof | |
| CN109135252B (en) | Degradable TPU film and preparation process thereof | |
| CN104987592A (en) | Hydrophobic enhanced foamed polypropylene and polymer absorbent composite material and preparation method thereof | |
| Rossi et al. | Emerging opportunities in the valorisation of wheat bran byproduct as additive in polymer composite materials | |
| CN1827701A (en) | Wood-plastic biological filling and method for making same | |
| CN105949811A (en) | Biologically-synthesized resin capable of controlling interfacial compatibility and application thereof | |
| CN111019251A (en) | Preparation method of inorganic nanoparticle-doped bio-based composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170613 |