CN106867093A - Military rotational moulding firearms pack composite material special - Google Patents
Military rotational moulding firearms pack composite material special Download PDFInfo
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- CN106867093A CN106867093A CN201710154707.1A CN201710154707A CN106867093A CN 106867093 A CN106867093 A CN 106867093A CN 201710154707 A CN201710154707 A CN 201710154707A CN 106867093 A CN106867093 A CN 106867093A
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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
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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
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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
- 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
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention provides a kind of military rotational moulding firearms packaging composite material special, with good anti-ultraviolet ageing performance, and intensity is higher, and combination property is superior.There is preferable resistance to UV aging energy through the modified peanut shell powder such as silane coupler, allyl sulfide and through the modified powdered rice hulls such as silane coupler, methyl orange and composite obtained in LLDPE, under prolonged ultraviolet irradiation, the break-draw strain retention rate of material is higher, and the dispersiveness of peanut shell powder after modified and powdered rice hulls in base polyethylene is preferably.But some particles can be produced using rotomoulded articles surface obtained in this composite, the performance and outward appearance of finished product is influenceed.After being digested to peanut shell powder and powdered rice hulls using a small amount of cellulase, this problem is resolved, and the amounts of particles of product surface is substantially reduced, and product surface becomes smooth.
Description
Technical field
The present invention relates to packaging material, more particularly to military rotational moulding firearms packaging composite material special.
Background technology
With the high speed development of high polymer material technology, various plastics and its composite substitute wood, gold more and more
Traditional firearms packaging material such as category and be applied in firearms packaging.Firearms packaging is the reliable and secure transport of firearms, loads and unloads and use
Guarantee, it is desirable to intensity is high, be unlikely to deform, anti-drop is excellent.Compared with other traditional firearms packaging material, plastics have strong
The superior combination properties such as degree is high, environmental suitability is strong, structure design is simple, light weight, recoverable, pack into firearms
The main flow of material.
The features such as polyethylene kind macromolecular material has good cheap, processing technology, light weight durable, has been widely used
In making firearms plastics package.Because there is side chain, double bond etc. " weakness " in its own structure, make in the synthesis of outside environmental elements
Can occur under aging, macroscopically cause variation, the cosmetic variation of mechanical property, it is microcosmic on be presented as knot product, oxidation, crosslinking,
The structure change such as branched and composition transfer.Especially solar radiation it is strong, dry, Seasonal Temperature Difference is big, relative humidity is low, drop
Under the weather conditions such as water rareness, generation is more easy to aging.
The content of the invention
It is an object of the invention to provide a kind of military rotational moulding firearms packaging composite material special, with good resistance to ultraviolet
Ageing properties, and intensity is higher, combination property is superior.
To achieve the above object, the technical scheme that the present invention is provided is as follows：
Military rotational moulding firearms pack composite material special, including following weight parts raw material：
LLDPE 100-120 parts, high density polyethylene (HDPE) 10-15 parts, 0.5-1.2 parts of modified peanut powder,
Modified 0.2-0.6 parts, crosslinking agent 0.1-0.5 parts, antioxidant 0.05-0.1 parts of powdered rice hulls；
The LLDPE is a kind of public product, commercially available, and general density is 0.93-0.94g/
cm3, melt flow rate (MFR) is 2-20g/10min.
The high density polyethylene (HDPE) density is 0.95-0.97g/cm3, melt flow rate (MFR) 5-20g/10min.
The crosslinking agent is cumyl peroxide.
The antioxidant is antioxidant 1010, and it is white crystalline powder, and chemical property stabilization can be widely applied to general
In the industries such as plastics, engineering plastics, synthetic rubber, fiber, PUR, resin, oil product, ink, coating.
The preparation method of the modified peanut powder is：
(1) peanut shell powder is dissipated with the moisture of 5-8 times of its weight, adjusts pH4.0-4.5, cellulase is added, in 40-45
DEG C enzymolysis 10-20min, then go out enzyme 6-8min at 90-95 DEG C；
(2) the 3- aminopropyls three of peanut shell powder weight 5-10% are added in the peanut shell powder enzymolysis liquid for obtaining to step (1)
Ethoxysilane coupling agent, 100-120min is stood after stirring, and obtains pretreated peanut shell powder enzymolysis liquid；
(3) to addition glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetraacetic in pretreated peanut shell powder enzymolysis liquid
Acetic acid, neopelex, 50-60 DEG C is heated to after stirring, and is subsequently adding iron chloride, 2- naphthylamines, diallyl
Thioether, potassium rhodanate, 50-60 DEG C of holding 2-4h, are filtered after being cooled to room temperature, and filter residue and drying to moisture ＜ 10% is crushed
400 mesh sieves are crossed afterwards, obtain final product modified peanut powder.
The peanut shell powder is the powdered granule formed after being crushed by pulverizer by drying peanut shell (peanut shell).
Peanut shell has abundant source as the leftover bits and pieces of agricultural product in China.Contain substantial amounts of organic compound in peanut shell, such as
Lignin, cellulose, pectin etc..
The cellulase is 1 with the mass ratio of peanut shell powder：200-300, the vigor of cellulase is 85U/g.
The consumption of the glycine is the 10-15% of peanut shell powder weight；The consumption of the pentaerythrite is peanut shell powder
The 0.1-0.5% of weight；The consumption of the methyl hydroxybenzoate is the 0.1-0.3% of peanut shell powder weight；The ethylenediamine tetra-acetic acid
Consumption for peanut shell powder weight 0.5-1.5%；The consumption of the neopelex is the 10- of peanut shell powder weight
20%；The consumption of the iron chloride is the 5-10% of peanut shell powder weight；The consumption of the 2- naphthylamines is peanut shell powder weight
1-3%；The consumption of the allyl sulfide is the 0.1-0.3% of peanut shell powder weight；The consumption of the potassium rhodanate is flower
The 3-8% of raw shell powder weight.
The preparation method of the modified powdered rice hulls is：
(1) powdered rice hulls are dissipated with the moisture of 3-5 times of its weight, adjusts pH4.0-4.5, cellulase is added, at 40-45 DEG C
Enzymolysis 10-20min, then gone out enzyme 6-8min at 90-95 DEG C, and pH to 7-8 is adjusted after the enzyme that goes out；
(2) the silane coupler a171 of powdered rice hulls weight 5-10% is added in the powdered rice hulls enzymolysis liquid for obtaining to step (1),
70-80min is stood after stirring, pretreated powdered rice hulls enzymolysis liquid is obtained；
(3) to addition trimethylolethane, enuatrol, pyrroles, cetyl three in pretreated powdered rice hulls enzymolysis liquid
Ammonio methacrylate, methyl orange, 5-10 DEG C of standing 1-3h, filtering, filter residue and drying cross 400 mesh to moisture ＜ 10% after crushing
Sieve, obtains final product modified powdered rice hulls.
The powdered rice hulls are crushed by dried rice husk and are obtained.
The cellulase is 1 with the mass ratio of powdered rice hulls：100-150, the vigor of cellulase is 85U/g.
The consumption of the trimethylolethane is 1.5-2 times of powdered rice hulls weight；The consumption of the enuatrol is powdered rice hulls
The 5-10% of weight；The consumption of the pyrroles is the 0.5-1% of powdered rice hulls weight；The use of the hexadecyltrimethylammonium chloride
It is the 3-6% of powdered rice hulls weight to measure；The consumption of the methyl orange is the 5-10% of powdered rice hulls weight.
The preparation method of the military rotational moulding firearms packaging composite material special is：High density polyethylene (HDPE) is low close with linear
Degree polyethylene is crushed to 30-50 mesh in advance, then mixes 1-2min in high-speed mixer with crosslinking agent；Add modified peanut
Shell powder, modified powdered rice hulls and antioxidant, and mix 5-10min in high-speed mixer, then at 180-200 DEG C, turn through screw rod
Speed is 200-500rpm extruding pelletizations, is obtained final product.
Inventor is found surprisingly that during research polyethylene and composite material of plant fiber, through silane coupler,
The modified peanut shell powder such as allyl sulfide and low close with linear through the modified powdered rice hulls such as silane coupler, methyl orange
Composite obtained in degree polyethylene has preferable resistance to UV aging energy, under prolonged ultraviolet irradiation, material
Break-draw strain retention rate is higher, and the dispersiveness of peanut shell powder after modified and powdered rice hulls in base polyethylene compared with
It is good.But some particles can be produced using rotomoulded articles surface obtained in this composite, the performance and outward appearance of finished product is influenceed.
After being digested to peanut shell powder and powdered rice hulls using a small amount of cellulase, this problem is resolved, product surface
Amounts of particles is substantially reduced, and product surface becomes smooth.
Obtained military rotational moulding firearms of the invention pack composite material special tensile strength in 16.1-16.8MPa, simply supported beam
Notch impact strength (23 DEG C) is in 67-68kJ/m2.The addition of modified peanut powder and modified powdered rice hulls is unsuitable excessive, otherwise
Its dispersiveness in base polyethylene can be influenceed, so as to influence the properties of product of rotomoulded articles.
The advantage of the invention is that：On the premise of mechanical property is ensured, the ultraviolet aging resistance of product is significantly improved
Can, and peanut shell and rice husk wide material sources, belong to string, safety and environmental protection, and cost is relatively low.
Specific embodiment
Embodiment 1：Military rotational moulding firearms pack composite material special, including following weight parts raw material：
105 parts of LLDPE, 12 parts of high density polyethylene (HDPE), 0.8 part of modified peanut powder, modified powdered rice hulls
0.3 part, 0.2 part of cumyl peroxide, 0.06 part of antioxidant 1010；
The preparation method of the modified peanut powder is：
(1) peanut shell powder is dissipated with the moisture of 6 times of its weight, adjusts pH4.2, add cellulase, in 45 DEG C of enzymolysis
15min, then go out enzyme 8min at 95 DEG C；
(2) ethoxy of 3- aminopropyls three of peanut shell powder weight 8% is added in the peanut shell powder enzymolysis liquid for obtaining to step (1)
Base silane coupling agent, 110min is stood after stirring, and obtains pretreated peanut shell powder enzymolysis liquid；
(3) to addition glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetraacetic in pretreated peanut shell powder enzymolysis liquid
Acetic acid, neopelex, are heated to 55 DEG C after stirring, be subsequently adding iron chloride, 2- naphthylamines, diallyl sulphur
Ether, potassium rhodanate, 55 DEG C of holding 3h, filter after being cooled to room temperature, and filter residue and drying crosses 400 to moisture ＜ 10% after crushing
Mesh sieve, obtains final product modified peanut powder.
The cellulase is 1 with the mass ratio of peanut shell powder：240, the vigor of cellulase is 85U/g.
The consumption of the glycine is the 12% of peanut shell powder weight；The consumption of the pentaerythrite is peanut shell powder weight
0.2%；The consumption of the methyl hydroxybenzoate is the 0.2% of peanut shell powder weight；The consumption of the ethylenediamine tetra-acetic acid is peanut
The 1% of shell powder weight；The consumption of the neopelex is the 15% of peanut shell powder weight；The consumption of the iron chloride
It is the 6% of peanut shell powder weight；The consumption of the 2- naphthylamines is the 2% of peanut shell powder weight；The use of the allyl sulfide
Measure is the 0.2% of peanut shell powder weight；The consumption of the potassium rhodanate is the 6% of peanut shell powder weight.
The preparation method of the modified powdered rice hulls is：
(1) powdered rice hulls are dissipated with the moisture of 4 times of its weight, adjusts pH4.0, add cellulase, in 40 DEG C of enzymolysis
15min, then gone out enzyme 6min at 90 DEG C, and pH to 7 is adjusted after the enzyme that goes out；
(2) the silane coupler a171 of powdered rice hulls weight 8% is added in the powdered rice hulls enzymolysis liquid for obtaining to step (1), is stirred
Uniform rear standing 75min is mixed, pretreated powdered rice hulls enzymolysis liquid is obtained；
(3) to addition trimethylolethane, enuatrol, pyrroles, cetyl three in pretreated powdered rice hulls enzymolysis liquid
Ammonio methacrylate, methyl orange, 6 DEG C of standing 2h, filtering, filter residue and drying cross 400 mesh sieves, i.e., to moisture ＜ 10% after crushing
Must be modified powdered rice hulls.
The cellulase is 1 with the mass ratio of powdered rice hulls：120, the vigor of cellulase is 85U/g.
The consumption of the trimethylolethane is 1.8 times of powdered rice hulls weight；The consumption of the enuatrol is powdered rice hulls weight
The 6% of amount；The consumption of the pyrroles is the 0.7% of powdered rice hulls weight；The consumption of the hexadecyltrimethylammonium chloride is rice
The 4% of shell powder weight；The consumption of the methyl orange is the 9% of powdered rice hulls weight.
The preparation method of the military rotational moulding firearms packaging composite material special is：High density polyethylene (HDPE) is low close with linear
Degree polyethylene is crushed to 50 mesh in advance, then mixes 1min in high-speed mixer with crosslinking agent；Add modified peanut powder,
Modified powdered rice hulls and antioxidant, and mix 6min in high-speed mixer, then at 190 DEG C, through screw speed for 300rpm is squeezed
Go out granulation, obtain final product.
Embodiment 2：Military rotational moulding firearms pack composite material special, including following weight parts raw material：
100 parts of LLDPE, 10 parts of high density polyethylene (HDPE), 0.5 part of modified peanut powder, modified powdered rice hulls
0.2 part, 0.1 part of cumyl peroxide, 0.05 part of antioxidant 1010；
The preparation method of the modified peanut powder is：
(1) peanut shell powder is dissipated with the moisture of 8 times of its weight, adjusts pH4.5, add cellulase, in 45 DEG C of enzymolysis
20min, then go out enzyme 8min at 95 DEG C；
(2) second of 3- aminopropyls three of peanut shell powder weight 10% is added in the peanut shell powder enzymolysis liquid for obtaining to step (1)
TMOS coupling agent, 120min is stood after stirring, and obtains pretreated peanut shell powder enzymolysis liquid；
(3) to addition glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetraacetic in pretreated peanut shell powder enzymolysis liquid
Acetic acid, neopelex, are heated to 60 DEG C after stirring, be subsequently adding iron chloride, 2- naphthylamines, diallyl sulphur
Ether, potassium rhodanate, 60 DEG C of holding 4h, filter after being cooled to room temperature, and filter residue and drying crosses 400 to moisture ＜ 10% after crushing
Mesh sieve, obtains final product modified peanut powder.
The cellulase is 1 with the mass ratio of peanut shell powder：200, the vigor of cellulase is 85U/g.
The consumption of the glycine is the 10% of peanut shell powder weight；The consumption of the pentaerythrite is peanut shell powder weight
0.1%；The consumption of the methyl hydroxybenzoate is the 0.1% of peanut shell powder weight；The consumption of the ethylenediamine tetra-acetic acid is peanut
The 0.5% of shell powder weight；The consumption of the neopelex is the 10% of peanut shell powder weight；The use of the iron chloride
Measure is the 5% of peanut shell powder weight；The consumption of the 2- naphthylamines is the 1% of peanut shell powder weight；The allyl sulfide
Consumption is the 0.1% of peanut shell powder weight；The consumption of the potassium rhodanate is the 3% of peanut shell powder weight.
The preparation method of the modified powdered rice hulls is：
(1) powdered rice hulls are dissipated with the moisture of 5 times of its weight, adjusts pH4.5, add cellulase, in 45 DEG C of enzymolysis
20min, then gone out enzyme 8min at 95 DEG C, and pH to 8 is adjusted after the enzyme that goes out；
(2) the silane coupler a171 of powdered rice hulls weight 10% is added in the powdered rice hulls enzymolysis liquid for obtaining to step (1), is stirred
Uniform rear standing 80min is mixed, pretreated powdered rice hulls enzymolysis liquid is obtained；
(3) to addition trimethylolethane, enuatrol, pyrroles, cetyl three in pretreated powdered rice hulls enzymolysis liquid
Ammonio methacrylate, methyl orange, 10 DEG C of standing 3h, filtering, filter residue and drying cross 400 mesh sieves, i.e., to moisture ＜ 10% after crushing
Must be modified powdered rice hulls.
The cellulase is 1 with the mass ratio of powdered rice hulls：150, the vigor of cellulase is 85U/g.
The consumption of the trimethylolethane is 1.5 times of powdered rice hulls weight；The consumption of the enuatrol is powdered rice hulls weight
The 5% of amount；The consumption of the pyrroles is the 0.5% of powdered rice hulls weight；The consumption of the hexadecyltrimethylammonium chloride is rice
The 3% of shell powder weight；The consumption of the methyl orange is the 5% of powdered rice hulls weight.
The preparation method of the military rotational moulding firearms packaging composite material special is：High density polyethylene (HDPE) is low close with linear
Degree polyethylene is crushed to 50 mesh in advance, then mixes 2min in high-speed mixer with crosslinking agent；Add modified peanut powder,
Modified powdered rice hulls and antioxidant, and mix 10min in high-speed mixer, then at 200 DEG C, through screw speed for 500rpm is squeezed
Go out granulation, obtain final product.
Embodiment 3：Military rotational moulding firearms pack composite material special, including following weight parts raw material：
120 parts of LLDPE, 15 parts of high density polyethylene (HDPE), 1.2 parts of modified peanut powder, modified powdered rice hulls
0.6 part, 0.5 part of cumyl peroxide, 0.1 part of antioxidant 1010；
The preparation method of the modified peanut powder is：
(1) peanut shell powder is dissipated with the moisture of 5 times of its weight, adjusts pH4.0, add cellulase, in 40 DEG C of enzymolysis
10min, then go out enzyme 6min at 90 DEG C；
(2) ethoxy of 3- aminopropyls three of peanut shell powder weight 5% is added in the peanut shell powder enzymolysis liquid for obtaining to step (1)
Base silane coupling agent, 100min is stood after stirring, and obtains pretreated peanut shell powder enzymolysis liquid；
(3) to addition glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetraacetic in pretreated peanut shell powder enzymolysis liquid
Acetic acid, neopelex, are heated to 50 DEG C after stirring, be subsequently adding iron chloride, 2- naphthylamines, diallyl sulphur
Ether, potassium rhodanate, 50 DEG C of holding 2h, filter after being cooled to room temperature, and filter residue and drying crosses 400 to moisture ＜ 10% after crushing
Mesh sieve, obtains final product modified peanut powder.
The cellulase is 1 with the mass ratio of peanut shell powder：200, the vigor of cellulase is 85U/g.
The consumption of the glycine is the 15% of peanut shell powder weight；The consumption of the pentaerythrite is peanut shell powder weight
0.5%；The consumption of the methyl hydroxybenzoate is the 0.3% of peanut shell powder weight；The consumption of the ethylenediamine tetra-acetic acid is peanut
The 1.5% of shell powder weight；The consumption of the neopelex is the 20% of peanut shell powder weight；The use of the iron chloride
Measure is the 10% of peanut shell powder weight；The consumption of the 2- naphthylamines is the 3% of peanut shell powder weight；The allyl sulfide
Consumption is the 0.3% of peanut shell powder weight；The consumption of the potassium rhodanate is the 8% of peanut shell powder weight.
The preparation method of the modified powdered rice hulls is：
(1) powdered rice hulls are dissipated with the moisture of 3 times of its weight, adjusts pH4.0, add cellulase, in 40 DEG C of enzymolysis
10min, then gone out enzyme 6min at 90 DEG C, and pH to 7 is adjusted after the enzyme that goes out；
(2) the silane coupler a171 of powdered rice hulls weight 5% is added in the powdered rice hulls enzymolysis liquid for obtaining to step (1), is stirred
Uniform rear standing 70min is mixed, pretreated powdered rice hulls enzymolysis liquid is obtained；
(3) to addition trimethylolethane, enuatrol, pyrroles, cetyl three in pretreated powdered rice hulls enzymolysis liquid
Ammonio methacrylate, methyl orange, 5 DEG C of standing 1h, filtering, filter residue and drying cross 400 mesh sieves, i.e., to moisture ＜ 10% after crushing
Must be modified powdered rice hulls.
The cellulase is 1 with the mass ratio of powdered rice hulls：100, the vigor of cellulase is 85U/g.
The consumption of the trimethylolethane is 2 times of powdered rice hulls weight；The consumption of the enuatrol is powdered rice hulls weight
10%；The consumption of the pyrroles is the 1% of powdered rice hulls weight；The consumption of the hexadecyltrimethylammonium chloride is powdered rice hulls
The 6% of weight；The consumption of the methyl orange is the 10% of powdered rice hulls weight.
The preparation method of the military rotational moulding firearms packaging composite material special is：High density polyethylene (HDPE) is low close with linear
Degree polyethylene is crushed to 30 mesh in advance, then mixes 1min in high-speed mixer with crosslinking agent；Add modified peanut powder,
Modified powdered rice hulls and antioxidant, and mix 5min in high-speed mixer, then at 180 DEG C, through screw speed for 200rpm is squeezed
Go out granulation, obtain final product.
Comparative example 1：Military rotational moulding firearms pack composite material special, and the difference with embodiment 1 is：
The preparation method of the modified peanut powder is：
(1) peanut shell powder is dissipated with the moisture of 6 times of its weight, adjusts pH4.2, add cellulase, in 42 DEG C of enzymolysis
5min, then go out enzyme 8min at 90 DEG C；
(2) second of 3- aminopropyls three of peanut shell powder weight 12% is added in the peanut shell powder enzymolysis liquid for obtaining to step (1)
TMOS coupling agent, 100min is stood after stirring, and obtains pretreated peanut shell powder enzymolysis liquid；
(3) to addition glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetraacetic in pretreated peanut shell powder enzymolysis liquid
Acetic acid, neopelex, iron chloride, 2- naphthylamines, allyl sulfide, potassium rhodanate, 60 DEG C of heating 5h, are cooled to room
Filtered after temperature, filter residue and drying crosses 400 mesh sieves to moisture ＜ 10% after crushing, obtain final product modified peanut powder.
The cellulase is 1 with the mass ratio of peanut shell powder：180, the vigor of cellulase is 85U/g.
The consumption of the glycine is the 9% of peanut shell powder weight；The consumption of the pentaerythrite is peanut shell powder weight
0.6%；The consumption of the methyl hydroxybenzoate is the 0.4% of peanut shell powder weight；The consumption of the ethylenediamine tetra-acetic acid is peanut
The 0.4% of shell powder weight；The consumption of the neopelex is the 25% of peanut shell powder weight；The use of the iron chloride
Measure is the 3% of peanut shell powder weight；The consumption of the 2- naphthylamines is the 5% of peanut shell powder weight；The allyl sulfide
Consumption is the 0.5% of peanut shell powder weight；The consumption of the potassium rhodanate is the 2% of peanut shell powder weight.
The preparation method of the modified powdered rice hulls is：
(1) powdered rice hulls are dissipated with the moisture of 5 times of its weight, adjusts pH4.0, add cellulase, in 40 DEG C of enzymolysis
30min, then gone out enzyme 6min at 95 DEG C, and pH to 8 is adjusted after the enzyme that goes out；
(2) the silane coupler a171 of powdered rice hulls weight 8% is added in the powdered rice hulls enzymolysis liquid for obtaining to step (1), is stirred
Uniform rear standing 80min is mixed, pretreated powdered rice hulls enzymolysis liquid is obtained；
(3) to addition trimethylolethane, enuatrol, pyrroles, cetyl three in pretreated powdered rice hulls enzymolysis liquid
Ammonio methacrylate, methyl orange, 15 DEG C of standing 3h, filtering, filter residue and drying cross 400 mesh sieves, i.e., to moisture ＜ 10% after crushing
Must be modified powdered rice hulls.
The cellulase is 1 with the mass ratio of powdered rice hulls：200, the vigor of cellulase is 85U/g.
The consumption of the trimethylolethane is 1.2 times of powdered rice hulls weight；The consumption of the enuatrol is powdered rice hulls weight
The 4% of amount；The consumption of the pyrroles is the 2% of powdered rice hulls weight；The consumption of the hexadecyltrimethylammonium chloride is rice husk
The 2% of powder weight；The consumption of the methyl orange is the 3% of powdered rice hulls weight.
Comparative example 2：Military rotational moulding firearms pack composite material special, and the difference with embodiment 1 is：
The preparation method of the modified peanut powder is：
(1) peanut shell powder is dissipated with the moisture of 6 times of its weight, adds the ethoxy of 3- aminopropyls three of peanut shell powder weight 8%
Base silane coupling agent, 110min is stood after stirring, and obtains pretreated peanut shell powder dispersion liquid；
(2) to addition glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetraacetic in pretreated peanut shell powder dispersion liquid
Acetic acid, neopelex, are heated to 55 DEG C after stirring, be subsequently adding iron chloride, 2- naphthylamines, diallyl sulphur
Ether, potassium rhodanate, 55 DEG C of holding 3h, filter after being cooled to room temperature, and filter residue and drying crosses 400 to moisture ＜ 10% after crushing
Mesh sieve, obtains final product modified peanut powder.
The preparation method of the modified powdered rice hulls is：
(1) powdered rice hulls are dissipated with the moisture of 4 times of its weight, adds the silane coupler a171 of powdered rice hulls weight 8%, stirring
75min is stood after uniform, pretreated powdered rice hulls dispersion liquid is obtained；
(2) to addition trimethylolethane, enuatrol, pyrroles, cetyl three in pretreated powdered rice hulls dispersion liquid
Ammonio methacrylate, methyl orange, 6 DEG C of standing 2h, filtering, filter residue and drying cross 400 mesh sieves, i.e., to moisture ＜ 10% after crushing
Must be modified powdered rice hulls.
Comparative example 3：Military rotational moulding firearms pack composite material special, and the difference with embodiment 1 is：
The preparation method of the modified peanut powder is：
(1) peanut shell powder is dissipated with the moisture of 6 times of its weight, adjusts pH4.2, add cellulase, in 45 DEG C of enzymolysis
15min, then go out enzyme 8min at 95 DEG C；
(2) ethoxy of 3- aminopropyls three of peanut shell powder weight 8% is added in the peanut shell powder enzymolysis liquid for obtaining to step (1)
Base silane coupling agent, 110min is stood after stirring, and obtains pretreated peanut shell powder enzymolysis liquid；
(3) to addition glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetraacetic in pretreated peanut shell powder enzymolysis liquid
Acetic acid, neopelex, are heated to 55 DEG C after stirring, be subsequently adding iron chloride, 2- naphthylamines, diallyl sulphur
Ether, 55 DEG C of holding 3h, filters after being cooled to room temperature, and filter residue and drying crosses 400 mesh sieves to moisture ＜ 10% after crushing, obtain final product
Modified peanut powder.
Comparative example 4：Military rotational moulding firearms pack composite material special, including following weight parts raw material：
105 parts of LLDPE, 12 parts of high density polyethylene (HDPE), 0.8 part of peanut shell powder, 0.3 part of powdered rice hulls, peroxide
Change 0.2 part of diisopropylbenzene (DIPB), 0.06 part of antioxidant 1010；
The peanut shell powder and powdered rice hulls are dried to moisture ＜ 10%, and 400 mesh sieves are crossed after crushing.
The preparation method of the military rotational moulding firearms packaging composite material special is：High density polyethylene (HDPE) is low close with linear
Degree polyethylene is crushed to 50 mesh in advance, then mixes 1min in high-speed mixer with crosslinking agent；Add peanut shell powder, rice husk
Powder and antioxidant, and mix 6min in high-speed mixer, it is 300rpm extruding pelletizations through screw speed, i.e., then at 190 DEG C
.
Experiment 1：Ultraviolet ageing is tested:With reference to GB/T 14522-2008 regulations, condition is used to irradiate 4h, 50 DEG C for 60 DEG C
Cooling 4h, so circulation, the break-draw strain retention rate of test material.
Break-draw strain (%) under each embodiment of the table 1 difference ultraviolet ageing time
Experiment 2：250g embodiments 1-3 is taken respectively and composite obtained in comparative example 1-3 puts into 100 × 100 × 100mm
Square mould in, it is machining through rotational moulding.Working process parameter is:350 DEG C of oven temperature, rotating speed 7rpm, during heating
Between 40min, cool time 30min.A fixed plane of 100 × 100mm is chosen after taking out rotomoulded articles, face center of making even
The heart chooses the plane of 10 × lOmm, observes and measure the amounts of particles of the plane.
The amounts of particles of each embodiment product surface of table 2 compares
The military rotational moulding firearms packaging composite material special ageing-resistant performance of embodiment 1-3 is best, and obtained rotational moulding system
Product surface is smooth without particle.The technical scheme parameter of comparative example 3 is not (in the modified of peanut shell powder in the range of the present invention is recorded
During be not added with potassium rhodanate), obtained composite ageing-resistant performance is had a greatly reduced quality, the powdered rice hulls of comparative example 2 and peanut shell
Powder is digested, obtained composite ageing-resistant performance not as good as embodiment 1-3, and rotomoulded articles surface particles quantity compared with
It is many.
Claims (5)
1. military rotational moulding firearms pack composite material special, it is characterised in that：Raw material including following weight parts：
LLDPE 100-120 parts, high density polyethylene (HDPE) 10-15 parts, it is 0.5-1.2 parts of modified peanut powder, modified
Powdered rice hulls 0.2-0.6 parts, crosslinking agent 0.1-0.5 parts, antioxidant 0.05-0.1 parts；
The crosslinking agent is cumyl peroxide；The antioxidant is antioxidant 1010.
2. military rotational moulding firearms as claimed in claim 1 pack composite material special, it is characterised in that：The military rotational moulding rifle
Tool packaging composite material special preparation method be：High density polyethylene (HDPE) and LLDPE are crushed to 30- in advance
50 mesh, then mix 1-2min with crosslinking agent in high-speed mixer；Add modified peanut powder, modified powdered rice hulls and antioxygen
Agent, and mix 5-10min in high-speed mixer, it is that 200-500rpm extrusions are made through screw speed then at 180-200 DEG C
Grain, obtains final product.
3. military rotational moulding firearms as claimed in claim 1 pack composite material special, it is characterised in that：The modified peanut
The preparation method of powder is：
(1) peanut shell powder is dissipated with the moisture of 5-8 times of its weight, adjusts pH4.0-4.5, cellulase is added, in 40-45 DEG C of enzyme
Solution 10-20min, then go out enzyme 6-8min at 90-95 DEG C；
(2) ethoxy of 3- aminopropyls three of peanut shell powder weight 5-10% is added in the peanut shell powder enzymolysis liquid for obtaining to step (1)
Base silane coupling agent, 100-120min is stood after stirring, and obtains pretreated peanut shell powder enzymolysis liquid；
(3) in pretreated peanut shell powder enzymolysis liquid add glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetra-acetic acid,
Neopelex, 50-60 DEG C is heated to after stirring, be subsequently adding iron chloride, 2- naphthylamines, allyl sulfide,
Potassium rhodanate, 50-60 DEG C of holding 2-4h, is cooled to after room temperature and filters, filter residue and drying to moisture ＜ 10%, mistake after crushing
400 mesh sieves, obtain final product modified peanut powder；
The cellulase is 1 with the mass ratio of peanut shell powder：200-300, the vigor of cellulase is 85U/g；
The consumption of the glycine is the 10-15% of peanut shell powder weight；The consumption of the pentaerythrite is peanut shell powder weight
0.1-0.5%；The consumption of the methyl hydroxybenzoate is the 0.1-0.3% of peanut shell powder weight；The use of the ethylenediamine tetra-acetic acid
It is the 0.5-1.5% of peanut shell powder weight to measure；The consumption of the neopelex is the 10- of peanut shell powder weight
20%；The consumption of the iron chloride is the 5-10% of peanut shell powder weight；The consumption of the 2- naphthylamines is peanut shell powder weight
1-3%；The consumption of the allyl sulfide is the 0.1-0.3% of peanut shell powder weight；The consumption of the potassium rhodanate is flower
The 3-8% of raw shell powder weight；
The preparation method of the modified powdered rice hulls is：
(1) powdered rice hulls are dissipated with the moisture of 3-5 times of its weight, adjusts pH4.0-4.5, add cellulase, in 40-45 DEG C of enzymolysis
10-20min, then gone out enzyme 6-8min at 90-95 DEG C, and pH to 7-8 is adjusted after the enzyme that goes out；
(2) the silane coupler a171 of powdered rice hulls weight 5-10%, stirring are added in the powdered rice hulls enzymolysis liquid for obtaining to step (1)
70-80min is stood after uniform, pretreated powdered rice hulls enzymolysis liquid is obtained；
(3) to addition trimethylolethane, enuatrol, pyrroles, cetyl trimethyl in pretreated powdered rice hulls enzymolysis liquid
Ammonium chloride, methyl orange, 5-10 DEG C of standing 1-3h, filtering, filter residue and drying cross 400 mesh sieves, i.e., to moisture ＜ 10% after crushing
Must be modified powdered rice hulls；
The cellulase is 1 with the mass ratio of powdered rice hulls：100-150, the vigor of cellulase is 85U/g；
The consumption of the trimethylolethane is 1.5-2 times of powdered rice hulls weight；The consumption of the enuatrol is powdered rice hulls weight
5-10%；The consumption of the pyrroles is the 0.5-1% of powdered rice hulls weight；The consumption of the hexadecyltrimethylammonium chloride is
The 3-6% of powdered rice hulls weight；The consumption of the methyl orange is the 5-10% of powdered rice hulls weight.
4. military rotational moulding firearms as claimed in claim 3 pack composite material special, it is characterised in that：The modified peanut
The preparation method of powder is：
(1) peanut shell powder is dissipated with the moisture of 6 times of its weight, adjusts pH4.2, add cellulase, 15min are digested at 45 DEG C,
Then go out enzyme 8min at 95 DEG C；
(2) the 3- aminopropyl-triethoxy silicon of peanut shell powder weight 8% is added in the peanut shell powder enzymolysis liquid for obtaining to step (1)
Alkane coupling agent, 110min is stood after stirring, and obtains pretreated peanut shell powder enzymolysis liquid；
(3) in pretreated peanut shell powder enzymolysis liquid add glycine, pentaerythrite, methyl hydroxybenzoate, ethylenediamine tetra-acetic acid,
Neopelex, is heated to 55 DEG C after stirring, be subsequently adding iron chloride, 2- naphthylamines, allyl sulfide, sulphur cyanogen
Change potassium, 55 DEG C of holding 3h are filtered after being cooled to room temperature, and filter residue and drying crosses 400 mesh sieves, i.e., to moisture ＜ 10% after crushing
Obtain modified peanut powder；
The cellulase is 1 with the mass ratio of peanut shell powder：240, the vigor of cellulase is 85U/g；
The consumption of the glycine is the 12% of peanut shell powder weight；The consumption of the pentaerythrite is peanut shell powder weight
0.2%；The consumption of the methyl hydroxybenzoate is the 0.2% of peanut shell powder weight；The consumption of the ethylenediamine tetra-acetic acid is peanut shell
The 1% of powder weight；The consumption of the neopelex is the 15% of peanut shell powder weight；The consumption of the iron chloride is
The 6% of peanut shell powder weight；The consumption of the 2- naphthylamines is the 2% of peanut shell powder weight；The consumption of the allyl sulfide
It is the 0.2% of peanut shell powder weight；The consumption of the potassium rhodanate is the 6% of peanut shell powder weight；
The preparation method of the modified powdered rice hulls is：
(1) powdered rice hulls are dissipated with the moisture of 4 times of its weight, adjusts pH4.0, add cellulase, digest 15min at 40 DEG C, so
Gone out enzyme 6min at 90 DEG C afterwards, and pH to 7 is adjusted after the enzyme that goes out；
(2) the silane coupler a171 of powdered rice hulls weight 8% is added in the powdered rice hulls enzymolysis liquid for obtaining to step (1), stirring is equal
75min is stood after even, pretreated powdered rice hulls enzymolysis liquid is obtained；
(3) to addition trimethylolethane, enuatrol, pyrroles, cetyl trimethyl in pretreated powdered rice hulls enzymolysis liquid
Ammonium chloride, methyl orange, 6 DEG C of standing 2h, filtering, filter residue and drying cross 400 mesh sieves, obtain final product and change to moisture ＜ 10% after crushing
Property powdered rice hulls；
The cellulase is 1 with the mass ratio of powdered rice hulls：120, the vigor of cellulase is 85U/g；
The consumption of the trimethylolethane is 1.8 times of powdered rice hulls weight；The consumption of the enuatrol is powdered rice hulls weight
6%；The consumption of the pyrroles is the 0.7% of powdered rice hulls weight；The consumption of the hexadecyltrimethylammonium chloride is powdered rice hulls
The 4% of weight；The consumption of the methyl orange is the 9% of powdered rice hulls weight.
5. military rotational moulding firearms as claimed in claim 1 pack composite material special, it is characterised in that：Including following raw materials：
LLDPE, high density polyethylene (HDPE), modified peanut powder, modified powdered rice hulls, crosslinking agent, antioxidant.
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