CN110204901A - A kind of preparation method of high impact polymers - Google Patents
A kind of preparation method of high impact polymers Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C08J9/0085—Use of fibrous compounding ingredients
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C—CHEMISTRY; METALLURGY
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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
Abstract
The present invention provides a kind of preparation methods of high impact polymers characterized by comprising by a certain amount of nano-tourmaline powder and nano-cellulose colloid, mixed in hydrochloric acid, forms tourmaline colloid；A certain amount of silane coupling agent is mixed with hydroxy silicon oil, catalyst, forms silicon substrate dispersion liquid；A certain amount of tourmaline colloid, silicon substrate dispersion liquid, plasticizer are mixed, premix high polymer is formed；Premix high polymer is put into foaming mould and is sealed, high impact polymers are made using supercritical fluid fretting map technology.Compared with existing similar product, the present invention uses new material, and prepared product has the characteristics that excellent in cushion effect, health properties are good, is suitable for production human body protective materials.
Description
Technical field
The present invention relates to a kind of preparation methods of high impact polymers to belong to especially suitable for making human body protective materials
In field of new materials.
Background technique
Human body inevitably will receive the injury such as collision, friction during exercise, especially such as ride, skidding, ice and snow contest fortune
It is dynamic, special protective clothing equipment must be worn to enhance protection.Blade inserting protector currently on the market mainly has the helmet, Protector for knee or elbow, shield
Waist, ankle guard etc. mostly use greatly the foamed materials such as EVA, XPE, synthetic rubber to be made, although can alleviate to a certain extent to people
The injury of body, but there is also hard, impact strength is poor, aptamer is poor the problems such as.In recent years, occurs shear thickening in the world
High polymer, the product can generate impact strength when by external force, and external force speed is faster, generated shock resistance is strong
Degree is higher, is the ideal material for developing human body protector.Shear thickening high polymer mainly by decentralized medium and disperses phase composition, wherein
Common decentralized medium mainly has polyethylene glycol etc.；Common dispersed phase mainly has silica dioxide granule, polyvinyl chloride particles, gathers
Two diluted acid methacrylate particles of methyl, carbon nano-fiber, titanium dioxide granule etc., wherein silica is the most commonly used.Publication No. CN
The patent of invention of 102926211 A, CN104327795 A are disclosed using the inorganic grain such as nano silica, nano montmorillonite
Son is the method that dispersed phase prepares shear thickening high polymer.
Tourmaline powder be after tourmaline raw ore impurity elimination through obtained powder is mechanically pulverized, containing to the beneficial B, F of human body,
Sr, Li et al. element, negative ion production with higher and far infrared transmissivity, and can anti-electromagnetic radiation, be a kind of ideal
Health-care material.The patent of invention of Publication No. CN 101982205A disclose a kind of tourmaline health-care products production method and
It is applied, and incorporates in silica gel after specially crushing tourmaline and sheet material is made, then sheet material is fixed in fabric pad, and pass through electricity
Heat generating device heats entire sheet material, so that the tourmaline particle in sheet material be promoted to release energy, forms health-care efficacy.Electricity
Gas mountain flour and silica belong to inorganic material, develop human body protective gear material by dispersed phase of tourmaline powder, rise to human body
While to protective action, the functionality such as health care, anti-electromagnetic radiation are also had both, there is preferable application space.But tourmaline is
A kind of silicate of complexity, chemical formula are Na (Mg, Fe, Mn, Li, Al)3Al6[Si6O18][BO3]3(OH,F)4, and silica
Chemical formula is SiO2, the chemical component of the two is different, and the hardness of tourmaline powder is high, density is big thus existing with titanium dioxide
Silicon is the shear thickening high polymer preparation method of dispersed phase, is not particularly suited for tourmaline powder, is badly in need of developing new preparation method.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of high impact polymers, replace nanometer with nano-tourmaline powder
Silica solves the problems, such as that existing preparation method can not be suitable for nano-tourmaline powder, develops a kind of healthcare function that has both
High impact polymers.
In order to achieve the above object, the present invention provides a kind of preparation methods of high impact polymers, which is characterized in that
It include: by least one of nano-tourmaline powder, nano silica, nano montmorillonite powder and nano mica powder and nanometer
Cellulose colloid and mixed in hydrochloric acid form tourmaline colloid；Silane coupling agent is mixed with hydroxy silicon oil and catalyst, forms silicon
Base dispersion liquid；Tourmaline colloid, silicon substrate dispersion liquid and plasticizer are mixed, premix high polymer is formed, premix high polymer is used
High impact polymers are made in supercritical fluid fretting map technology.
Preferably, the specification of the nano-tourmaline powder, nano silica, nano montmorillonite powder and nano mica powder
For 12500-20000 mesh.
Preferably, in the nano-cellulose colloid, the length of nano-cellulose is 80~150nm, diameter is 3~
8nm；The mass ratio of nano-cellulose is 1.8wt%-2.2wt%.
Preferably, the concentration of hydrochloric acid is 10%-30%.
Preferably, the tourmaline colloid the preparation method comprises the following steps: by mass ratio be 40wt%-45wt% nanometer it is electrical
Mountain flour, mass ratio is the nano-cellulose colloid of 47wt%-55wt%, after mass ratio is the mixed in hydrochloric acid of 5wt%-8wt%,
High speed disperser is used at room temperature, and 20~30min is dispersed with 12000~16000rpm revolving speed, forms tourmaline colloid.
Preferably, the catalyst is the polyurethane organotin catalysts that tin mass ratio is 18wt%-19wt%.
Preferably, the silicon substrate dispersion liquid the preparation method comprises the following steps: by mass ratio be 10wt%-20wt% it is silane coupled
Agent, mass ratio is the hydroxy silicon oil of 75wt%-88wt%, after the catalyst mixing that mass ratio is 2wt%-5wt%, in room temperature-
High speed disperser is used at 60 DEG C, and 10~20min is dispersed with 12000~16000rpm revolving speed, forms silicon substrate dispersion liquid.
Preferably, the premix high polymer the preparation method comprises the following steps: being respectively the electrical of 28wt%-40wt% by mass ratio
The plasticizer mixing of stone colloid, the silicon substrate dispersion liquid of 55wt%-70wt%, 2wt%-5wt%, using height at -60 DEG C of room temperature
Fast dispersion machine disperses 20~30min with 12000~16000rpm revolving speed, forms premix high polymer.
Preferably, the supercritical fluid fretting map technology include: will premix high polymer be put into it is in foaming mould and close
Mold is sealed, supercritical fluid is filled in foaming mould, mold is warming up to 100-110 DEG C, and heating rate is 10-20 DEG C/min；
Pressurize 2-3MPa, compression rate 0.2-0.5MPa/min；10-30min is stood after reaching predetermined temperature and pressure, then rapidly will
Temperature is reduced to room temperature, and rate of temperature fall is 20-30 DEG C/min, while the pressure in abrupt release mold, premix high polymer are rapid
Expansion opens mold at once and continues to expand after it is full of die space, until volume stability, it is poly- to form high impact-resistant
Close object.
It is highly preferred that the volume ratio of the foaming mould and premix high polymer is 2:1-10:1.
It is highly preferred that the supercritical fluid is supercritical CO2。
Preferably, the density of the high impact polymers is 30-80kg/m3, Falling ball impact strength 15-20kN,
Infrared emittance is 88%-92%.
Preferably, the preparation method of the nano-cellulose colloid includes: to use agricultural crop straw for raw material, through alkalinity
Dicyandiamide solution processing, then be mechanically pulverized to obtain stalk fibre powder；Stalk fibre powder is placed in TEMPO oxidation system
It is handled, obtains stalk fibre powder suspension, then carry out centrifugal treating again, decentralized processing obtains nano-cellulose glue
Body.
The agricultural crop straw is vegetalitas agricultural waste material, preferably rice straw, wheat stalk etc..
It is highly preferred that the basic solvent system is to contain NaOH and Na2SO3Aqueous solution, NaOH concentration be 15~
25g/L、Na2SO3Concentration is 10~20g/L, and the processing time is 1~3h, temperature is 100~120 DEG C, and bath raio is 1:10~1:20.
It is highly preferred that the mechanical crushing in the first step is the stalk fibre that will be obtained after the processing of basic solvent system
It is crushed using pulverizer, crosses 40-60 mesh, obtain stalk fibre powder.
It is highly preferred that it is 0.01~0.02g/L that the proportion of the TEMPO oxidation system, which is TEMPO concentration, NaClO is dense
Degree is 100~200g/L, and NaBr concentration is 0.1~0.2g/L, processing method are as follows: stalk fibre powder is placed in TEMPO oxidation
In system, bath raio is 1:30~1:50, stirs 4~10h under the conditions of 2~6 DEG C with 500~1000rpm revolving speed, obtains stalk fibre
Tie up powder suspension.
It is highly preferred that the centrifugal treating are as follows: stalk fibre powder suspension is placed in supercentrifuge, with 5000
~8000rpm revolving speed is centrifuged 5~10min, removes supernatant liquor and adds distilled water, repeats above-mentioned steps until pH of suspension
Value obtains stalk fibre sediment to neutrality.
It is highly preferred that the decentralized processing are as follows: stalk fibre sediment is used high speed dispersion at a temperature of 2~6 DEG C
Machine disperses 5~10min with 12000~16000rpm revolving speed, obtains nano-cellulose colloid.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is using nano-tourmaline powder and nano-cellulose colloid admixture as dispersed phase, silane coupling agent and carboxylic
Base silicone oil is decentralized medium, develops a kind of premix high polymer with shear thickening effect, and utilize the micro- hair of supercritical fluid
High impact polymers are made in bubble technology.Nano-tourmaline powder has preferable healthcare function, mixed with nano-cellulose colloid
Close, and hydrochloric acid be added as auxiliary agent, can be improved the uniformly dispersed of nano-tourmaline powder and its and decentralized medium combination it is firm
Solidity；The impact resistance and resistant of high or low temperature that product can be improved as decentralized medium are mixed with hydroxy silicon oil using silane coupling agent.
The present invention using nano-tourmaline powder with health care function replace nano silica, and with silane coupling agent with
Hydroxy silicon oil mixing is used as decentralized medium, and compared with existing similar product, the present invention uses new material, and prepared product has
Excellent in cushion effect, the features such as health properties are good, is suitable for production human body protective materials.
Specific embodiment
Present invention will be further explained below with reference to specific examples.Nano-tourmaline powder used in following embodiment is
The production of Lingshou County Wo Ao mineral products processing factory, model 325, specification are 15000 mesh；Stalk derives from Songjiang District in Shanghai City farm；
The chemical reagent such as hydrochloric acid, polyurethane organotin catalysts, silane coupling agent can be in Aladdin reagent (Shanghai) Co., Ltd.
Purchase；Hydroxy silicon oil is bought in Ji Peng fluosilicic Materials Co., Ltd, Shenzhen, model JP-35；Plasticizer is in Hangzhou Gui Chang section
The purchase of skill Co., Ltd, model GCZ-7001；Blender is the production of Shanghai Si Le Instrument Ltd., 81-2 type；PH meter is
Upper Nereid Ke Lei magnetic instrument plant production, PHS-3C type；High speed disperser is the production of IKA company, Germany, T25Ultra-turrax
Type；Centrifuge is Anting Scientific Instrument Factory, Shanghai's production, TDL-5-A type；Foaming mould is autoclave, Weihai roc prestige precision instrument
Co., Ltd's production, GSHA-1L type.
Falling ball impact strength in following embodiment is tested according to " EN/BS EN 1621-1-2012 ", infrared emittance according to
It is tested according to " detection and evaluation of GB/T 30127-2013 textile far infrared performance ".
Embodiment 1 prepares Cellulose nanocrystal palpus
Use rice straw for raw material, handled in basic solvent system, basic solvent system be containing NaOH and
Na2SO3Aqueous solution, by by NaOH and Na2SO3It is dissolved in water obtained, matching as NaOH concentration is 20g/L, Na2SO3It is dense
Degree is 15g/L；The processing time is 2h, temperature is 110 DEG C, bath raio 1:10；Being disposed, it is clean to take out, in 60 DEG C of vacuum drying ovens
Constant weight is arrived in middle drying；Purified treated rice straw fiber is crushed using pulverizer, crosses 50 meshes, obtains rice straw fibre
Tie up powder；Rice straw fiber dust is placed in TEMPO oxidation system, the TEMPO oxidation system by by TEMPO,
NaClO, NaBr are dissolved in water obtained, match as 0.02g/L TEMPO, 150g/L NaClO, 0.15g/L NaBr, bath raio is
1:30, adjusting mixed solution pH value with 1%NaOH is 10.5；Gained mixture is placed in blender, under the conditions of 4 DEG C with
600rpm revolving speed stirs 5h, obtains stalk fibre powder suspension；Stalk fibre powder suspension is placed in supercentrifuge,
It is centrifuged 6min with 6000rpm revolving speed, remove supernatant liquor and adds distilled water, repeat above-mentioned centrifugation, removal supernatant liquor and is added
The step 5 time of distilled water, until suspension pH value to neutrality, obtains stalk fibre sediment；By stalk fibre sediment at 4 DEG C
At a temperature of use high speed disperser, with 15000rpm revolving speed disperse 5min, obtain nano-cellulose colloid, the matter of nano-cellulose
Amount is than being 2%.The nano-cellulose colloid length for using transmissioning electric mirror test to prepare is 3~8nm for 80~150nm, diameter.
Embodiment 2
A kind of preparation method of high impact polymers, specific steps are as follows:
Step 1: by mass ratio is 40wt% nano-tourmaline powder and mass ratio is 5wt% hydrochloric acid (concentration 30%),
Mass ratio be 55% embodiment 1 made from nano-cellulose colloid mixing, be put into high speed disperser, at room temperature with
12000rpm revolving speed disperses 30min, forms tourmaline colloid；
Step 2: by the silane coupling agent (model KH-560) that mass ratio is 10wt% and the hydroxyl that mass ratio is 88wt%
Base silicone oil, the polyurethane organotin catalysts that mass ratio is 2wt% (No. CAS is 301-10-0) mixing, are put into high speed disperser,
20min is dispersed with 12000rpm revolving speed at 40 DEG C, forms silicon substrate dispersion liquid；
Step 3: by mass ratio be 28wt% tourmaline colloid and mass ratio be 70wt% silicon substrate dispersion liquid, quality
Than the plasticizer mixing for 2wt%, it is put into high speed disperser, 30min is dispersed with 12000rpm revolving speed at 40 DEG C, forms premix
High polymer；
Step 4: premix high polymer is put into foaming mould, the volume ratio of mold and premix high polymer is 3:1, sealing
Mold；CO is filled in foaming mould2Supercritical fluid, mold are warming up to 100 DEG C, and heating rate is 10 DEG C/min；Pressurization
3MPa, compression rate 0.3MPa/min；10min is stood after reaching predetermined temperature and pressure, then temperature is reduced to room rapidly
Temperature, rate of temperature fall is 20 DEG C/min, while the pressure in abrupt release mold, premix high polymer expand rapidly, are full of mould to it
After having space, mold is opened at once and continues to expand, until volume stability, forms high impact polymers.High impact-resistant is poly-
The density for closing object is 75.3kg/m3, Falling ball impact strength 15.1kN, infrared emittance 91.3%.
Embodiment 3
A kind of preparation method of high impact polymers, specific steps are as follows:
Step 1: by mass ratio is 45wt% nano-tourmaline powder and mass ratio is 8wt% hydrochloric acid (concentration 30%),
Mass ratio be 47% embodiment 1 made from nano-cellulose colloid mixing, be put into high speed disperser, at room temperature with
16000rpm revolving speed disperses 20min, forms tourmaline colloid；
Step 2: by the silane coupling agent (model KH-560) that mass ratio is 20wt% and the hydroxyl that mass ratio is 75wt%
Base silicone oil, the polyurethane organotin catalysts that mass ratio is 5wt% (No. CAS is 301-10-0) mixing, are put into high speed disperser,
10min is dispersed with 16000rpm revolving speed at 50 DEG C, forms silicon substrate dispersion liquid；
Step 3: by mass ratio be 40wt% tourmaline colloid and mass ratio be 55wt% silicon substrate dispersion liquid, quality
Than the plasticizer mixing for 5wt%, it is put into high speed disperser, 20min is dispersed with 16000rpm revolving speed at 50 DEG C, forms premix
High polymer；
Step 4: premix high polymer is put into foaming mould, the volume ratio of mold and premix high polymer is 10:1, sealing
Mold；CO is filled in foaming mould2Supercritical fluid, mold are warming up to 110 DEG C, and heating rate is 20 DEG C/min；Pressurization
2MPa, compression rate 0.4MPa/min；20min is stood after reaching predetermined temperature and pressure, then temperature is reduced to room rapidly
Temperature, rate of temperature fall is 30 DEG C/min, while the pressure in abrupt release mold, premix high polymer expand rapidly, are full of mould to it
After having space, mold is opened at once and continues to expand, until volume stability, forms high impact polymers.High impact-resistant is poly-
The density for closing object is 31.6kg/m3, Falling ball impact strength 19.7kN, infrared emittance 89.2%.
The used technological parameter of above-described embodiment is only preferable parameter of the invention, implementation not for the purpose of limiting the invention
Range.Those skilled in the art are easy to modify to parameter of the invention, and described herein general former
It ought to be used in other application example.Those skilled in the art's announcement according to the present invention, improves the present invention and repairs
Changing all should be within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high impact polymers characterized by comprising by nano-tourmaline powder, nanometer titanium dioxide
At least one of silicon, nano montmorillonite powder and nano mica powder and nano-cellulose colloid and mixed in hydrochloric acid are formed electrical
Stone colloid；Silane coupling agent is mixed with hydroxy silicon oil and catalyst, forms silicon substrate dispersion liquid；By tourmaline colloid, silicon substrate point
Dispersion liquid and plasticizer mixing, form premix high polymer, and highly resistance is made using supercritical fluid fretting map technology in premix high polymer
Impact polymer.
2. the preparation method of high impact polymers as described in claim 1, which is characterized in that the nano-tourmaline
Powder, nano silica, the specification of nano montmorillonite powder and nano mica powder are 12500-20000 mesh.
3. the preparation method of high impact polymers as described in claim 1, which is characterized in that the nano-cellulose glue
In body, the length of nano-cellulose is 80~150nm, and diameter is 3~8nm；The mass ratio of nano-cellulose is 1.8wt%-
2.2wt%.
4. the preparation method of high impact polymers as described in claim 1, which is characterized in that the tourmaline colloid
The preparation method comprises the following steps: the nano-tourmaline powder for being 40wt%-45wt% by mass ratio, mass ratio is the nanometer of 47wt%-55wt%
Cellulose colloid uses high speed disperser after mass ratio is the mixed in hydrochloric acid of 5wt%-8wt% at room temperature, with 12000~
16000rpm revolving speed disperses 20~30min, forms tourmaline colloid.
5. the preparation method of high impact polymers as described in claim 1, which is characterized in that the silicon substrate dispersion liquid
The preparation method comprises the following steps: the silane coupling agent for being 10wt%-20wt% by mass ratio, mass ratio is the hydroxyl silicon of 75wt%-88wt%
Oil uses high speed disperser after the catalyst mixing that mass ratio is 2wt%-5wt% at -60 DEG C of room temperature, with 12000~
16000rpm revolving speed disperses 10~20min, forms silicon substrate dispersion liquid.
6. the preparation method of high impact polymers as described in claim 1, which is characterized in that the premix high polymer
The preparation method comprises the following steps: by mass ratio be respectively the tourmaline colloid of 28wt%-40wt%, 55wt%-70wt% silicon substrate dispersion liquid,
The plasticizer of 2wt%-5wt% mixes, and high speed disperser is used at -60 DEG C of room temperature, with the dispersion of 12000~16000rpm revolving speed
20~30min forms premix high polymer.
7. the preparation method of high impact polymers as described in claim 1, which is characterized in that the supercritical fluid is micro-
Foaming technique includes: that premix high polymer is put into foaming mould simultaneously sealed mold, and supercritical fluid is filled in foaming mould,
Mold is warming up to 100-110 DEG C, and heating rate is 10-20 DEG C/min；Pressurize 2-3MPa, compression rate 0.2-0.5MPa/
min；10-30min is stood after reaching predetermined temperature and pressure, then temperature is reduced to room temperature, rate of temperature fall 20-30 rapidly
DEG C/min, while the pressure in abrupt release mold, premix high polymer are expanded rapidly, after it is full of die space, are beaten at once
Mold continues to expand, until volume stability, forms high impact polymers.
8. the preparation method of high impact polymers as described in claim 1, which is characterized in that the high impact-resistant polymerization
The density of object is 30-80kg/m3, Falling ball impact strength 15-20kN, infrared emittance 88%-92%.
9. the preparation method of high impact polymers as described in claim 1, which is characterized in that the nano-cellulose glue
The preparation method of body includes: to use agricultural crop straw for raw material, is handled through basic solvent system, then is mechanically pulverized to obtain straw
Stalk fiber powder；Stalk fibre powder is placed in TEMPO oxidation system and is handled, stalk fibre powder suspension is obtained,
Then centrifugal treating is carried out again, decentralized processing obtains nano-cellulose colloid.
10. the preparation method of high impact polymers as claimed in claim 9, which is characterized in that the basic solvent body
System is to contain NaOH and Na2SO3Aqueous solution, NaOH concentration be 15~25g/L, Na2SO3Concentration is 10~20g/L, when processing
Between for 1~3h, temperature be 100~120 DEG C, bath raio is 1:10~1:20；The mechanical crushing is will be through basic solvent system
The stalk fibre obtained after processing is crushed using pulverizer, is crossed 40-60 mesh, is obtained stalk fibre powder；The TEMPO oxygen
It is 0.01~0.02g/L that the proportion of change system, which is TEMPO concentration, and NaClO concentration is 100~200g/L, NaBr concentration is 0.1~
0.2g/L, processing method are as follows: stalk fibre powder is placed in TEMPO oxidation system, bath raio is 1:30~1:50, at 2~6 DEG C
Under the conditions of with 500~1000rpm revolving speed stir 4~10h, obtain stalk fibre powder suspension；The centrifugal treating are as follows: will
Stalk fibre powder suspension is placed in supercentrifuge, is centrifuged 5~10min with 5000~8000rpm revolving speed, removal upper layer is clear
Liquid simultaneously plus distilled water, repeat above-mentioned steps until suspension pH value to neutrality, obtain stalk fibre sediment；Point
Dissipate processing are as follows: stalk fibre sediment is used into high speed disperser at a temperature of 2~6 DEG C, with 12000~16000rpm revolving speed point
5~10min is dissipated, nano-cellulose colloid is obtained.
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| CN201910397989.7A CN110204901A (en) | 2019-05-14 | 2019-05-14 | A kind of preparation method of high impact polymers |
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| CN201910397989.7A CN110204901A (en) | 2019-05-14 | 2019-05-14 | A kind of preparation method of high impact polymers |
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Application publication date: 20190906 |