CN108641256A - A kind of preparation process of shuck wood plastic composite - Google Patents
A kind of preparation process of shuck wood plastic composite Download PDFInfo
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- CN108641256A CN108641256A CN201810465119.4A CN201810465119A CN108641256A CN 108641256 A CN108641256 A CN 108641256A CN 201810465119 A CN201810465119 A CN 201810465119A CN 108641256 A CN108641256 A CN 108641256A
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- shuck
- preparation process
- plastic composite
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- 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
Abstract
The invention discloses a kind of preparation processes of shuck wood plastic composite, are related to Wood-plastic material field, steps are as follows：The crushing of shuck carries out surface modification after microwave combustion method and alkali process, using silane coupling agent, is uniformly mixed with polymer methacrylic resin and other filler auxiliary agents, compression molding is carried out with vulcanizing press；In preparation process of the present invention by carrying out microwave combustion method, alkali process and the compound pretreatments of coupling agent KH550 to shuck after, there is good cohesive force and interface compatibility with macromolecule resin, the mechanical property for enhancing Wood-plastic material, the product being prepared have good mechanical property and electromagnetic wave shielding.
Description
Technical field
The present invention relates to Wood-plastic material fields, and in particular to a kind of preparation process of shuck wood plastic composite.
Background technology
Nut is a classification of indehiscent fruit, and pericarp is hard, includes 1 or more seeds.Nutriment is abundant, albumen
Matter, grease, minerals, vitamin are higher, and to human development, building up health and preventing disease has fabulous effect, have certain
Medical value.It is just being increasingly subject to the welcome of people and is liking, output sends out amplitude increase year by year.
In nut is edible, the shell weight of nut accounts for more larger, and nutrient content is relatively low, direct processing and eating at
Divide seldom, falls generally as offal treatment.It is very unrestrained if not being used containing a large amount of lignins, cellulose in shuck
Take.
Invention content
For problems of the prior art, the present invention provides a kind of preparation works of shuck wood plastic composite
Skill, by carrying out microwave combustion method, alkali process and the compound pretreatments of coupling agent KH550 to shuck in preparation process of the present invention
Afterwards, there is good cohesive force and interface compatibility with macromolecule resin, enhances the mechanical property of Wood-plastic material, is prepared
Product have good mechanical property and electromagnetic wave shielding.
In order to achieve the above object, the present invention is achieved through the following technical solutions：
A kind of preparation process of shuck wood plastic composite, includes the following steps：
(1) shuck is put into pulverizer and is crushed, after crossing 150-200 mesh sieve, with deionized water according to 1:5 matter
It measures ratio after mixing, is put into micro-wave oven, microwave water-bath heat treatment is carried out, by 3-5 microwave treatment, when per treatment
Between be 5 minutes, filtering；
(2) sodium hydroxide solution for preparing 8%, by the shuck powder after microwave treatment in step (1) according to mass ratio 1:5
In mixed dissolution to sodium hydroxide solution, it is warming up to 40-50 degrees Celsius, after impregnating 2-5 hours, was cleaned repeatedly with deionized water
Filter residue is placed in vacuum drying chamber by filter until filtrate pH value is less than 7.1, dry abjection moisture；
(3) heavily fortified point after coupling agent KH550 absolute ethyl alcohol dilution wiring solution-formings, being uniformly sprayed at after step (2) drying
It on shell powder, is placed in after disperseing 15-30 minutes in ultrasonic dispersing machine, places 12-16 hours, be put into vacuum drying chamber
It is 4-6 hours dry under conditions of 110-115 degrees Celsius；
(4) after being stirred methacrylic resin and initiator, a certain amount of nano-calcium carbonate, carbon nanometer is added
It is quiet after pipe, chitosan, carbon fiber, microfine diatomaceous, β-damascone, coconut shell flour made from step (3) are uniformly mixed
It sets 40-60 minutes；
(5) mixture in step (4) is allowed such as compression molding in vulcanizing press, demoulding, be cooled to room temperature to get.
Preferably, the microwave water-bath in the step (1) carries out under middle fire screen.
Preferably, the dry removing moisture in the step (2) is the dry 15-20 under 110 degrees Celsius of vacuum condition
Hour.
Preferably, the dosage of the coupling agent KH550 in the step (3) is the 2-4% of shuck weight.
Preferably, coupling agent KH550 is diluted with absolute ethyl alcohol according to 1 in the step (3):7 quality compares mixed diluting.
Preferably, methacrylic resin in the step (4), initiator, nano-calcium carbonate, carbon nanotube, chitosan,
Carbon fiber, microfine diatomaceous, β-damascone, coconut shell flour made from step (3) quality proportioning be 60-70:1.5-2.5:
10-15:8-15:2-4:4-7:5-10:2-4:30-40。
Preferably, the initiator be peroxidating di tert butyl carbonate, cumyl peroxide, peroxidized t-butyl perbenzoate and
One or more of peroxidating trimethylacetic acid tertiary butyl ester combines.
Preferably, being uniformly mixed as under 50-60 degrees Celsius in the step (4), with 800-1500 revs/min
Speed, be stirred 20-30 minutes.
Preferably, the compression molding in the step (5) is specially to be forced into 13-15MPa under 150-160 degrees Celsius, is protected
Pressure 8-12 minutes.
The present invention has following advantageous effect：
(1) compound by carrying out microwave combustion method, alkali process and coupling agent KH550 to shuck in preparation process of the present invention
After pretreatment, there is good cohesive force and interface compatibility with macromolecule resin, enhance the mechanical property of Wood-plastic material, make
Product made of standby has good mechanical property and electromagnetic wave shielding.
(2) by more to program treated shuck, the structure of hemicellulose and lignin in shuck is destroyed.So that fibre
It ties up cellulose content relative increase and cellulose crystallity increases, to enhance the rigidity and mechanical property of lignin material.
(3) use die press technology for forming in present invention process, preparation can methacrylic resin and shuck powder wood moulding it is multiple
Condensation material improves electromagnetic wave shielding, heat resistance and the mechanical property of composite material by carbon nanotube and carbon fiber.
(4) it uses microfine diatomaceous and nano-calcium carbonate as filler in preparation process of the present invention, there is toughened and reinforced work
With improving the bending strength and the modulus of elasticity in static bending of composite material, heat distortion temperature and dimensional stability, be effectively improved material
Processing performance and mechanical property.
Specific implementation mode
The specific implementation mode of the present invention is further described with reference to embodiment, following embodiment is only used for more
Technical scheme of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
Embodiment 1
A kind of preparation process of shuck wood plastic composite, includes the following steps：
(1) shuck is put into pulverizer and is crushed, after crossing 150 mesh sieve, with deionized water according to 1:5 mass ratio
After mixing, it is put into micro-wave oven, carries out microwave water-bath heat treatment, by 3 microwave treatments, the time per treatment is 5
Minute, filtering；
(2) sodium hydroxide solution for preparing 8%, by the shuck powder after microwave treatment in step (1) according to mass ratio 1:5
In mixed dissolution to sodium hydroxide solution, 40 degrees Celsius are warming up to, after impregnating 2 hours, cleans filtering repeatedly with deionized water, until
Until filtrate pH value is less than 7.1, filter residue is placed in vacuum drying chamber, dry abjection moisture；
(3) heavily fortified point after coupling agent KH550 absolute ethyl alcohol dilution wiring solution-formings, being uniformly sprayed at after step (2) drying
It on shell powder, is placed in after disperseing 15 minutes in ultrasonic dispersing machine, places 12 hours, be put into Celsius 110 in vacuum drying chamber
It is 4 hours dry under conditions of degree；
(4) after being stirred methacrylic resin and initiator, a certain amount of nano-calcium carbonate, carbon nanometer is added
It is quiet after pipe, chitosan, carbon fiber, microfine diatomaceous, β-damascone, coconut shell flour made from step (3) are uniformly mixed
It sets 40 minutes；
(5) mixture in step (4) is allowed such as compression molding in vulcanizing press, demoulding, be cooled to room temperature to get.
Microwave water-bath in step (1) carries out under middle fire screen.
Dry removing moisture in step (2) is the drying 15 hours under 110 degrees Celsius of vacuum condition.
The dosage of coupling agent KH550 in step (3) is the 2% of shuck weight.
Coupling agent KH550 is diluted with absolute ethyl alcohol according to 1 in step (3):7 quality compares mixed diluting.
It is methacrylic resin in step (4), initiator, nano-calcium carbonate, carbon nanotube, chitosan, carbon fiber, ultra-fine
Diatomite, β-damascone, coconut shell flour made from step (3) quality proportioning be 60:1.5:10:8:2:4:5:2:30.
Initiator is peroxidating di tert butyl carbonate.
Being uniformly mixed at 50 c, with 800 revs/min of speed, to be stirred 20 points in step (4)
Clock.
Compression molding in step (5) is specially to be forced into 13MPa, pressurize 8 minutes under 150 degrees Celsius.
Embodiment 2
A kind of preparation process of shuck wood plastic composite, includes the following steps：
(1) shuck is put into pulverizer and is crushed, after crossing 200 mesh sieve, with deionized water according to 1:5 mass ratio
After mixing, it is put into micro-wave oven, carries out microwave water-bath heat treatment, by 5 microwave treatments, the time per treatment is 5
Minute, filtering；
(2) sodium hydroxide solution for preparing 8%, by the shuck powder after microwave treatment in step (1) according to mass ratio 1:5
In mixed dissolution to sodium hydroxide solution, 50 degrees Celsius are warming up to, after impregnating 5 hours, cleans filtering repeatedly with deionized water, until
Until filtrate pH value is less than 7.1, filter residue is placed in vacuum drying chamber, dry abjection moisture；
(3) heavily fortified point after coupling agent KH550 absolute ethyl alcohol dilution wiring solution-formings, being uniformly sprayed at after step (2) drying
It on shell powder, is placed in after disperseing 30 minutes in ultrasonic dispersing machine, places 16 hours, be put into Celsius 115 in vacuum drying chamber
It is 6 hours dry under conditions of degree；
(4) after being stirred methacrylic resin and initiator, a certain amount of nano-calcium carbonate, carbon nanometer is added
It is quiet after pipe, chitosan, carbon fiber, microfine diatomaceous, β-damascone, coconut shell flour made from step (3) are uniformly mixed
It sets 60 minutes；
(5) mixture in step (4) is allowed such as compression molding in vulcanizing press, demoulding, be cooled to room temperature to get.
Microwave water-bath in step (1) carries out under middle fire screen.
Dry removing moisture in step (2) is the drying 20 hours under 110 degrees Celsius of vacuum condition.
The dosage of coupling agent KH550 in step (3) is the 4% of shuck weight.
Coupling agent KH550 is diluted with absolute ethyl alcohol according to 1 in step (3):7 quality compares mixed diluting.
It is methacrylic resin in step (4), initiator, nano-calcium carbonate, carbon nanotube, chitosan, carbon fiber, ultra-fine
Diatomite, β-damascone, coconut shell flour made from step (3) quality proportioning be 70:2.5:15:15:4:7:10:4:40.
Initiator is cumyl peroxide.
Being uniformly mixed at 60 c, with 1500 revs/min of speed, to be stirred 30 in step (4)
Minute.
Compression molding in step (5) is specially to be forced into 15MPa, pressurize 12 minutes under 160 degrees Celsius.
Embodiment 3
A kind of preparation process of shuck wood plastic composite, includes the following steps：
(1) shuck is put into pulverizer and is crushed, after crossing 180 mesh sieve, with deionized water according to 1:5 mass ratio
After mixing, it is put into micro-wave oven, carries out microwave water-bath heat treatment, by 4 microwave treatments, the time per treatment is 5
Minute, filtering；
(2) sodium hydroxide solution for preparing 8%, by the shuck powder after microwave treatment in step (1) according to mass ratio 1:5
In mixed dissolution to sodium hydroxide solution, 46 degrees Celsius are warming up to, after impregnating 3 hours, cleans filtering repeatedly with deionized water, until
Until filtrate pH value is less than 7.1, filter residue is placed in vacuum drying chamber, dry abjection moisture；
(3) heavily fortified point after coupling agent KH550 absolute ethyl alcohol dilution wiring solution-formings, being uniformly sprayed at after step (2) drying
It on shell powder, is placed in after disperseing 25 minutes in ultrasonic dispersing machine, places 14 hours, be put into Celsius 112 in vacuum drying chamber
It is 5 hours dry under conditions of degree；
(4) after being stirred methacrylic resin and initiator, a certain amount of nano-calcium carbonate, carbon nanometer is added
It is quiet after pipe, chitosan, carbon fiber, microfine diatomaceous, β-damascone, coconut shell flour made from step (3) are uniformly mixed
It sets 50 minutes；
(5) mixture in step (4) is allowed such as compression molding in vulcanizing press, demoulding, be cooled to room temperature to get.
Microwave water-bath in step (1) carries out under middle fire screen.
Dry removing moisture in step (2) is the drying 18 hours under 110 degrees Celsius of vacuum condition.
The dosage of coupling agent KH550 in step (3) is the 3% of shuck weight.
Coupling agent KH550 is diluted with absolute ethyl alcohol according to 1 in step (3):7 quality compares mixed diluting.
It is methacrylic resin in step (4), initiator, nano-calcium carbonate, carbon nanotube, chitosan, carbon fiber, ultra-fine
Diatomite, β-damascone, coconut shell flour made from step (3) quality proportioning be 65:2.2:13:12:3:6:8:3:32.
Initiator is peroxidized t-butyl perbenzoate.
Being uniformly mixed under 56 degrees Celsius, with 1100 revs/min of speed, to be stirred 28 in step (4)
Minute.
Compression molding in step (5) is specially to be forced into 13.5MPa, pressurize 11 minutes under 152 degrees Celsius.
Embodiment 4
A kind of preparation process of shuck wood plastic composite, includes the following steps：
(1) shuck is put into pulverizer and is crushed, after crossing 160 mesh sieve, with deionized water according to 1:5 mass ratio
After mixing, it is put into micro-wave oven, carries out microwave water-bath heat treatment, by 5 microwave treatments, the time per treatment is 5
Minute, filtering；
(2) sodium hydroxide solution for preparing 8%, by the shuck powder after microwave treatment in step (1) according to mass ratio 1:5
In mixed dissolution to sodium hydroxide solution, 44 degrees Celsius are warming up to, after impregnating 5 hours, cleans filtering repeatedly with deionized water, until
Until filtrate pH value is less than 7.1, filter residue is placed in vacuum drying chamber, dry abjection moisture；
(3) heavily fortified point after coupling agent KH550 absolute ethyl alcohol dilution wiring solution-formings, being uniformly sprayed at after step (2) drying
It on shell powder, is placed in after disperseing 18 minutes in ultrasonic dispersing machine, places 15 hours, be put into Celsius 112 in vacuum drying chamber
It is 6 hours dry under conditions of degree；
(4) after being stirred methacrylic resin and initiator, a certain amount of nano-calcium carbonate, carbon nanometer is added
It is quiet after pipe, chitosan, carbon fiber, microfine diatomaceous, β-damascone, coconut shell flour made from step (3) are uniformly mixed
It sets 50 minutes；
(5) mixture in step (4) is allowed such as compression molding in vulcanizing press, demoulding, be cooled to room temperature to get.
Microwave water-bath in step (1) carries out under middle fire screen.
Dry removing moisture in step (2) is the drying 18 hours under 110 degrees Celsius of vacuum condition.
Preferably, the dosage of the coupling agent KH550 in the step (3) is the 3.5% of shuck weight.
Coupling agent KH550 is diluted with absolute ethyl alcohol according to 1 in step (3):7 quality compares mixed diluting.
It is methacrylic resin in step (4), initiator, nano-calcium carbonate, carbon nanotube, chitosan, carbon fiber, ultra-fine
Diatomite, β-damascone, coconut shell flour made from step (3) quality proportioning be 67:2.1:12:14:3.5:5:8:3.5:
35。
Initiator is peroxidating trimethylacetic acid tertiary butyl ester.
Being uniformly mixed under 58 degrees Celsius, with 1350 revs/min of speed, to be stirred 28 in step (4)
Minute.
Compression molding in step (5) is specially to be forced into 14.5MPa, pressurize 10 minutes under 158 degrees Celsius.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although with reference to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features.All essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (9)
1. a kind of preparation process of shuck wood plastic composite, which is characterized in that include the following steps：
(1) shuck is put into pulverizer and is crushed, after crossing 150-200 mesh sieve, with deionized water according to 1:5 mass ratio
After mixing, it is put into micro-wave oven, carries out microwave water-bath heat treatment, by 3-5 microwave treatment, the time per treatment is
5 minutes, filtering；
(2) sodium hydroxide solution for preparing 8%, by the shuck powder after microwave treatment in step (1) according to mass ratio 1:5 mixing
It is dissolved into sodium hydroxide solution, is warming up to 40-50 degrees Celsius, after impregnating 2-5 hours, clean filtering repeatedly with deionized water,
Until filtrate pH value is less than 7.1, filter residue is placed in vacuum drying chamber, dry abjection moisture；
(3) shuck after coupling agent KH550 absolute ethyl alcohol dilution wiring solution-formings, being uniformly sprayed at after step (2) drying
It on powder, is placed in after disperseing 15-30 minutes in ultrasonic dispersing machine, places 12-16 hours, be put into vacuum drying chamber in 110-
It is 4-6 hours dry under conditions of 115 degrees Celsius；
(4) after being stirred methacrylic resin and initiator, a certain amount of nano-calcium carbonate, carbon nanotube, shell is added
After glycan, carbon fiber, microfine diatomaceous, β-damascone, coconut shell flour made from step (3) are uniformly mixed, 40- is stood
60 minutes；
(5) mixture in step (4) is allowed such as compression molding in vulcanizing press, demoulding, be cooled to room temperature to get.
2. the preparation process of shuck wood plastic composite according to claim 1, which is characterized in that the step (1)
In microwave water-bath carried out under middle fire screen.
3. the preparation process of shuck wood plastic composite according to claim 1, which is characterized in that the step (2)
In dry removing moisture be under 110 degrees Celsius of vacuum condition, it is 15-20 hours dry.
4. the preparation process of shuck wood plastic composite according to claim 1, which is characterized in that the step (3)
In coupling agent KH550 dosage be shuck weight 2-4%.
5. the preparation process of shuck wood plastic composite according to claim 4, which is characterized in that the step (3)
Middle coupling agent KH550 is diluted with absolute ethyl alcohol according to 1:7 quality compares mixed diluting.
6. the preparation process of shuck wood plastic composite according to claim 1, which is characterized in that the step (4)
Middle methacrylic resin, initiator, nano-calcium carbonate, carbon nanotube, chitosan, carbon fiber, microfine diatomaceous, β-dihydro are big
The quality proportioning of coconut shell flour made from horse ketone, step (3) is 60-70:1.5-2.5:10-15:8-15:2-4:4-7:5-10:2-
4:30-40。
7. the preparation process of shuck wood plastic composite according to claim 6, which is characterized in that the initiator is
One in peroxidating di tert butyl carbonate, cumyl peroxide, peroxidized t-butyl perbenzoate and peroxidating trimethylacetic acid tertiary butyl ester
Kind or several combinations.
8. the preparation process of shuck wood plastic composite according to claim 1, which is characterized in that the step (4)
In be uniformly mixed under 50-60 degrees Celsius, with 800-1500 revs/min of speed, to be stirred 20-30 minutes.
9. the preparation process of shuck wood plastic composite according to claim 1, which is characterized in that the step (5)
In compression molding be specially to be forced into 13-15MPa, pressurize 8-12 minutes under 150-160 degrees Celsius.
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| CN201810465119.4A CN108641256A (en) | 2018-05-16 | 2018-05-16 | A kind of preparation process of shuck wood plastic composite |
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| CN201810465119.4A CN108641256A (en) | 2018-05-16 | 2018-05-16 | A kind of preparation process of shuck wood plastic composite |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11046836B2 (en) * | 2019-10-18 | 2021-06-29 | Nutjobs | Formulations and products to replace single-use plastics and polystyrene with bio-benign materials such as agricultural wastes |
| US11230507B2 (en) * | 2019-10-18 | 2022-01-25 | Nutjobs | Formulations and products to replace single-use plastics and polystyrene with bio-benign materials such as agricultural wastes |
| US11434373B2 (en) | 2019-10-18 | 2022-09-06 | Nutjobs | Formulations and products to replace single-use plastics and polystyrene with bio-benign materials such as agricultural wastes |
| US11591474B2 (en) | 2019-10-18 | 2023-02-28 | Nutjobs | Formulations and products to replace single-use plastics and polystyrene with bio-benign materials such as agricultural wastes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11046836B2 (en) * | 2019-10-18 | 2021-06-29 | Nutjobs | Formulations and products to replace single-use plastics and polystyrene with bio-benign materials such as agricultural wastes |
| US11230507B2 (en) * | 2019-10-18 | 2022-01-25 | Nutjobs | Formulations and products to replace single-use plastics and polystyrene with bio-benign materials such as agricultural wastes |
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| US11591474B2 (en) | 2019-10-18 | 2023-02-28 | Nutjobs | Formulations and products to replace single-use plastics and polystyrene with bio-benign materials such as agricultural wastes |
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Application publication date: 20181012 |