CN109370133A - A kind of method of cellulose enhancing polymethyl methacrylate - Google Patents
A kind of method of cellulose enhancing polymethyl methacrylate Download PDFInfo
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- CN109370133A CN109370133A CN201811175300.8A CN201811175300A CN109370133A CN 109370133 A CN109370133 A CN 109370133A CN 201811175300 A CN201811175300 A CN 201811175300A CN 109370133 A CN109370133 A CN 109370133A
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- polymethyl methacrylate
- prepolymerization
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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
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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 a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of methods of cellulose enhancing polymethyl methacrylate, belong to cellulose reinforcing material technical field.The following steps are included: S01, is broken into the wooden particle for wooden unit；S02 prepares delignification's solution, and the wooden particle is placed in above-mentioned delignification's solution simultaneously constantly boiling 4h or more, then impurity is removed with distilled water flushing, obtains the wooden particle I；The wooden particle I is placed in the H that mass fraction is 30% by S032O2In and ebuillition of heated, wherein the wooden particle I's is of low quality in H2O2The 30% of quality.Present invention aims at the mechanical strengths for improving polymethyl methacrylate, the PMMA transparent composite with the high optical transmittance of arbitrary dimension is made using modified lumber fibre and prepolymerization MMA solution, and wood fiber raw material is from a wealth of sources, can even sawdust processing waste material (such as sawdust and branch etc.) be used, it is low in cost, resource is saved, preparation efficiency is high.
Description
Technical field
The present invention relates to a kind of methods of cellulose enhancing polymethyl methacrylate, belong to cellulose reinforcing material technology
Field.
Background technique
In order to maintain the energy resources in the world and mitigate environmental pressure, the manufacture of green building has become that there is an urgent need to fast
The problem of speed reply.Harmless, sustainable material becomes the matter of priority in world's interests inventory, with methyl methacrylate
(MMA) organic glass for raw material production is passed with gradually replacing the advantages that its light weight, safe and non-toxic, good crush resistance
Application of the system unorganic glass in life, such as baby bottles, children bottle.But the product function produced only with single MMA
Energy property is single, and application place is limited, can be the extensive degree for further increasing its application by taking addition functional material.
As one of the most abundant biological material, timber has been widely used as tool, fuel and construction material.In timber
Cellulose, intensity is high, and elasticity is good, and due to its excellent optical transmittance and excellent thermal insulation, improved wood is
Start in energy-saving window.By the way that the cellulose of index matching is added into polymethyl methacrylate (PMMA), not only
Original high permeability can be kept, and improves the mechanical performance of window.But in current research, the wood sample size of addition
Very little and thinner thickness, because the preparation of existing transparent composite needs complete timber as substrate, and lignin is to connect
The key substance of wood cell is connect, therefore large-sized substrate is very easy to rupture during delignification acts on, and is extremely difficult to
Glass size size in practical application.And lumber thickness is bigger, and the difficulty of MMA solution impregnated timber increases, and impregnates endless
Plenary session increases the gap between MMA and timber, causes the transparent composite inner refractive index being prepared into inconsistent, and light decay occurs
Subtract phenomenon.Therefore, in the prior art, produce thick and solid, large-sized transparent composite and be very suitable to practical application.Therefore it is existing
The method that cellulose enhances polymethyl methacrylate, cellulosic material source are complete wood template, and there are manufacturing costs
The problems such as height, preparation efficiency are low, and the PMMA transparent composite produced is size-limited.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of cellulose enhancing polymethyl methacrylate method,
Purpose is the mechanical strength of raising polymethyl methacrylate (PMMA), utilizes modified lumber fibre and prepolymerization MMA
The PMMA transparent composite with the high optical transmittance of arbitrary dimension is made in solution, and wood fiber raw material is from a wealth of sources,
Can even sawdust processing waste material (such as sawdust and branch etc.) be used, it is low in cost, resource is saved, preparation efficiency is high.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of method of cellulose enhancing polymethyl methacrylate, comprising the following steps:
Wooden unit is broken into the wooden particle by S01；
S02 prepares delignification's solution, the wooden particle is placed in above-mentioned delignification's solution simultaneously constantly boiling 4h or more, then
Impurity is removed with distilled water flushing, obtains the wooden particle I；
The wooden particle I is placed in the H that mass fraction is 30% by S032O2In and ebuillition of heated, wherein the wooden particle I it is of low quality in
H2O2The wooden particle I is stirred into fiber and at least filters three with distilled water by the 30% of quality when all wood particle I become white
It is secondary, delignified lumber fibre is made；
Delignified lumber fibre is immersed in prepolymerization MMA solution by S04, and permeates at least 10 points under the vacuum pressures
Clock makes prepolymerization MMA solution be sufficiently impregnated delignified lumber fibre；
The lumber fibre being sufficiently impregnated is placed in the glass mold of different specification size by S05, heats 6h at 50 ~ 70 DEG C
Prepare PMMA transparent composite above.
The diameter of the wooden particle after smashing in S01 is 3-5mm.
Delignification's solution in S02 the preparation method comprises the following steps: the mass fraction of NaOH is 10%, Na2SO3Mass fraction be
5%, it is dissolved in distilled water and being made.
In S02, the wooden particle it is of low quality in the 30% of delignification's solution quality.
In S04, delignified lumber fibre is of low quality in the 30% of prepolymerization MMA solution quality.
It include initiator in prepolymerization MMA solution in S04.
The initiator is azodiisobutyronitrile, and the additional amount of the azodiisobutyronitrile is equivalent to prepolymerization MMA solution
The 0.3 ~ 0.5% of quality.
The prepolymerization MMA solution is under azodiisobutyronitrile effect, and pre-polymerization is bonded to solution in glycerol shape at 70 ~ 80 DEG C
Until, after prepolymerization, pre-polymer solution is quickly transferred to be cooled to room temperature termination reaction in ice-water bath.
The refractive index of the PMMA transparent composite and the refractive index of cellulose match.
The size for the glass mold that the present invention uses includes but is not limited to following size: 80mm × 25mm × 1mm, 80mm ×
25mm × 5mm and 300mm × 300mm × 10mm.
In the present invention, first the smashed wooden particle delignification is handled, it is dry under conditions of 105 ± 3 DEG C, it will dry
The wooden particulate samples afterwards are put into NaOH, Na2SO3It in delignification's solution of distilled water preparation, and keeps boiling, spend later
Ionized water rinses, then the dioxygen water process that sample mass fraction is 30% is stirred sample when all particles become white
It mixes fiber and (is extracted and then rinsed with deionized water) at least three times with distilled water suction filtration, it is fine that delignified timber is made
Dimension, lumber fibre is sufficiently impregnated in prepolymerization MMA solution, infiltrates the nano-cellulose fiber net on its chamber and cell wall,
It is transferred in glass mold and PMMA transparent composite is made.
The refractive index of lignin is 1.61, and the folding of cellulose (refractive index 1.53) and hemicellulose (refractive index ≈ 1.53)
It is relatively low to penetrate rate, after removing lignin, the refractive index of cell wall constituent is regarded as 1.53, the lumber fibre after removing lignin
Its refractive index is close with PMMA, adjusts optical interface with this, and the addition of lumber fibre can make the transparent composite wood of PMMA
Material has certain mist degree.
MMA in the present invention can act synergistically with the cellulose aligned on cell wall, therefore lumber fibre adds
After entering, mechanical property (high-intensitive and elasticity modulus) more single PMMA organic glass that PMMA transparent composite is shown is more
Well, light weight, at low cost, large-scale commercial production application preferably, prospect are very wide.
Compared with the prior art, the invention has the benefit that
(1) the invention enables the organic glass mechanical strength for using MMA to produce raisings；
(2) present invention prepares transparent composite simple process, and preparation efficiency is high, and the transparent composite of preparation is not by size
Limitation；
(3) transparent composite prepared by the present invention is not limited by raw material, and wood-curing waste, agricultural waste can be used
Deng low in cost, economize on resources, protect environment；
(4) transparent composite good transmittance produced by the invention, mist degree are high, can be used for protect the place of privacy.
The present invention is sufficiently impregnated by mixing prepolymerized MMA solution with delignified lumber fibre in MMA solution
Arbitrary dimension PMMA transparent composite is prepared after into lumber fibre.The PMMA transparent composite prepared by this method, no
Only maintain the high permeability of organic glass, and improve the mechanical strength of organic glass, at the same have certain mist degree so as to
It is used in the occasion for needing to protect privacy.Wood fiber raw material is from a wealth of sources, it might even be possible to (such as be sawed using sawdust processing waste material
End and branch etc.), it is low in cost, save resource.And this method can produce not size-limited PMMA transparent composite,
Compared with preparing transparent composite with complete wood template, preparation efficiency about improves three times, therefore, this method preparation
The large-scale commercial production application preferably of PMMA transparent composite, prospect are very wide.
Specific embodiment
The present invention will be further explained below.
Embodiment 1
A kind of method of cellulose enhancing polymethyl methacrylate, the steps include:
It (1) is 0.386g/cm by density3Poplar be broken into the wooden particle that diameter is about 3-5mm；
(2) Na for the NaOH and 5% for the use of mass fraction being 10%2SO3Delignification's solution is prepared in distilled water, will be equivalent to
The wooden particle of the 30% of delignification's solution quality is placed in one and constantly boiling 4h or more, then removes impurity with distilled water, i.e.,
Obtain the wooden particle I；
(3) the wooden particle I is placed in the H that mass fraction is 30%2O2In and keep boiling；It, will be wooden when all particles become white
Particle I stirs into fiber and is filtered three times with distilled water, and delignified lumber fibre is made；
(4) prepolymerization MMA solution is made using 2,2'-Azobis (2-methylpropionitrile) (i.e. azodiisobutyronitrile)
For initiator, under initiator effect at 80 DEG C prepolymerization 15 minutes；The additional amount of azodiisobutyronitrile is equivalent to prepolymerization
The 0.3% of MMA solution quality；
(5) prepolymerization MMA solution is quickly cooled to room temperature termination reaction in ice-water bath；
(6) delignified lumber fibre is immersed in prepolymerization MMA solution, and permeate under the vacuum pressures make within 10 minutes it is pre-
Polymerization MMA solution is sufficiently impregnated lumber fibre；The additional amount of delignified lumber fibre is equivalent to the matter of prepolymerization MMA solution
The 10% of amount；
(7) processed lumber fibre is placed on having a size of in 80mm × 25mm × 1mm glass mold, heats 8h at 60 DEG C
To prepare PMMA transparent composite.
After tested, PMMA transparent composite made from the present embodiment, light transmittance is up to 92%, close to the light transmittance of PMMA
(light transmittance of PMMA is 95%)；Mist degree is 56%；Elasticity modulus is that 2.2 GPa(PMMA elasticity modulus are 1.8 GPa)；It stretches strong
Degree is that 46.8 MPa(PMMA tensile strengths are 41.4 MPa).
Embodiment 2
The present embodiment and the difference of embodiment 1 are only that: in step (7), processed lumber fibre being placed on having a size of 80mm
In the glass mold of × 25mm × 5mm.
After tested, PMMA transparent composite made from the present embodiment, light transmittance is up to 83%；Mist degree is 72%；Springform
Amount is 2.2 GPa；Tensile strength is 46.8 MPa.
Embodiment 3
The present embodiment and the difference of embodiment 1 are only that: in step (7), processed lumber fibre being placed on having a size of 300mm
In the glass mold of × 300mm × 10mm.
After tested, PMMA transparent composite made from the present embodiment, light transmittance is up to 68%；Mist degree is 76%；Springform
Amount is 2.2 GPa；Tensile strength is 46.8 MPa.
Described in summary, the method for the present invention using cellulose enhancing polymethyl methacrylate, not only light transmittance
Well, there is certain mist degree, can be used for the place of particular needs protection privacy, while making the organic glass produced using MMA as raw material
Mechanical strength improves, and is of great significance to the preparation of large scale PMMA transparent composite, and the PMMA produced is transparent multiple
Condensation material is not size-limited.
Embodiment 4
A kind of method of cellulose enhancing polymethyl methacrylate, comprising the following steps:
Wooden unit is broken into the wooden particle by S01；The diameter of the wooden particle after smashing is 3 ~ 5mm or so；
The mass fraction of S02, NaOH are 10%, Na2SO3Mass fraction be 5%, be dissolved in distilled water be made delignification it is molten
The wooden particle is placed in above-mentioned delignification's solution and constantly boiling 10h, the quality of the wooden particle is delignification's solution quality by liquid
30%, then with distilled water flushing remove impurity, obtain the wooden particle I；
The wooden particle I is placed in the H that mass fraction is 30% by S032O2In and ebuillition of heated, wherein the quality of the wooden particle I be H2O2
The wooden particle I is stirred into fiber and is filtered four times with distilled water, is made by the 20% of quality when all wood particle I become white
Delignified lumber fibre；
S04, prepolymerization MMA solution use azodiisobutyronitrile as initiator, the prepolymerization at 70 DEG C under initiator effect
Until solution is in glycerol shape；The additional amount of azodiisobutyronitrile is equivalent to the 0.5% of prepolymerization MMA solution quality；Prepolymerization is complete
Pre-polymer solution is quickly transferred to be cooled to room temperature termination reaction in ice-water bath by Bi Hou；Delignified lumber fibre is soaked
Bubble permeates that be sufficiently impregnated prepolymerization MMA solution within 12 minutes delignified in prepolymerization MMA solution under the vacuum pressures
Lumber fibre；
The lumber fibre being sufficiently impregnated is placed in the glass mold of arbitrary dimension by S05, heats 15h at 50 DEG C to prepare
PMMA transparent composite.
It is preferable to retain mechanical strength for the present embodiment delignification that mechanical strength in timber and photopermeability is poor
Cellulose and MMA are mixed with polymethyl methacrylate (PMMA) transparent composite, are making organic glass using MMA
When, original light transmittance is not only maintained, while cellulose has certain mist degree in manufactured glass, is suitable for some guarantors
The occasion of privacy is protected, and the high resiliency of cellulose also plays the effect of reinforcing glass mechanical strength.
Embodiment 5
A kind of method of cellulose enhancing polymethyl methacrylate, comprising the following steps:
Wooden unit is broken into the wooden particle by S01；The diameter of the wooden particle after smashing is 3 ~ 5mm or so；
The mass fraction of S02, NaOH are 10%, Na2SO3Mass fraction be 5%, be dissolved in distilled water be made delignification it is molten
The wooden particle is placed in above-mentioned delignification's solution and constantly boiling 6h, the quality of the wooden particle is delignification's solution quality by liquid
20%, then with distilled water flushing remove impurity, obtain the wooden particle I；
The wooden particle I is placed in the H that mass fraction is 30% by S032O2In and ebuillition of heated, wherein the quality of the wooden particle I be H2O2
The wooden particle I is stirred into fiber and is filtered four times with distilled water, is made by the 10% of quality when all wood particle I become white
Delignified lumber fibre；
S04, prepolymerization MMA solution use azodiisobutyronitrile as initiator, the prepolymerization at 75 DEG C under initiator effect
Until solution is in glycerol shape；The additional amount of azodiisobutyronitrile is equivalent to the 0.4% of prepolymerization MMA solution quality；Prepolymerization is complete
Pre-polymer solution is quickly transferred to be cooled to room temperature termination reaction in ice-water bath by Bi Hou；Delignified lumber fibre is soaked
Bubble permeates that be sufficiently impregnated prepolymerization MMA solution within 15 minutes delignified in prepolymerization MMA solution under the vacuum pressures
Lumber fibre；
The lumber fibre being sufficiently impregnated is placed in the glass mold of arbitrary dimension by S05, heats 6h at 70 DEG C to prepare
PMMA transparent composite.
It is preferable to retain mechanical strength for the present embodiment delignification that mechanical strength in timber and photopermeability is poor
Cellulose and MMA are mixed with polymethyl methacrylate (PMMA) transparent composite, are making organic glass using MMA
When, original light transmittance is not only maintained, while cellulose has certain mist degree in manufactured glass, is suitable for some guarantors
The occasion of privacy is protected, and the high resiliency of cellulose also plays the effect of reinforcing glass mechanical strength.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of method of cellulose enhancing polymethyl methacrylate, it is characterised in that: the following steps are included:
Wooden unit is broken into the wooden particle by S01；
S02 prepares delignification's solution, the wooden particle is placed in above-mentioned delignification's solution simultaneously constantly boiling 4h or more, then
Impurity is removed with distilled water flushing, obtains the wooden particle I；
The wooden particle I is placed in the H that mass fraction is 30% by S032O2In and ebuillition of heated, wherein the wooden particle I it is of low quality in
H2O2The wooden particle I is stirred into fiber and at least filters three with distilled water by the 30% of quality when all wood particle I become white
It is secondary, delignified lumber fibre is made；
Delignified lumber fibre is immersed in prepolymerization MMA solution by S04, and permeates at least 10 points under the vacuum pressures
Clock makes prepolymerization MMA solution be sufficiently impregnated delignified lumber fibre；
The lumber fibre being sufficiently impregnated is placed in the glass mold of different specification size by S05, heats 6h at 50 ~ 70 DEG C
Prepare PMMA transparent composite above.
2. a kind of method of cellulose enhancing polymethyl methacrylate according to claim 1, it is characterised in that: S01
In smash after the wooden particle diameter be 3-5mm.
3. a kind of method of cellulose enhancing polymethyl methacrylate according to claim 1, it is characterised in that: S02
In delignification's solution the preparation method comprises the following steps: the mass fraction of NaOH be 10%, Na2SO3Mass fraction be 5%, be dissolved in distillation
It is made in water.
4. a kind of method of cellulose enhancing polymethyl methacrylate according to claim 1, it is characterised in that: S02
In, the wooden particle it is of low quality in the 30% of delignification's solution quality.
5. a kind of method of cellulose enhancing polymethyl methacrylate according to claim 1, it is characterised in that: S04
In, delignified lumber fibre is of low quality in the 30% of prepolymerization MMA solution quality.
6. a kind of method of cellulose enhancing polymethyl methacrylate according to claim 1, it is characterised in that: S04
In prepolymerization MMA solution in include initiator.
7. a kind of method of cellulose enhancing polymethyl methacrylate according to claim 6, it is characterised in that: described
Initiator is azodiisobutyronitrile, the additional amount of the azodiisobutyronitrile be equivalent to prepolymerization MMA solution quality 0.3 ~
0.5%。
8. a kind of method of cellulose enhancing polymethyl methacrylate according to claim 7, it is characterised in that: described
Prepolymerization MMA solution is under azodiisobutyronitrile effect, and pre-polymerization is bonded to solution in until glycerol shape at 70 ~ 80 DEG C, prepolymerization
After, pre-polymer solution is quickly transferred to be cooled to room temperature termination reaction in ice-water bath.
9. a kind of method of cellulose enhancing polymethyl methacrylate according to claim 1, it is characterised in that: described
The refractive index of PMMA transparent composite and the refractive index of cellulose match.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811175300.8A CN109370133B (en) | 2018-10-10 | 2018-10-10 | Method for reinforcing polymethyl methacrylate by cellulose |
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| CN201811175300.8A CN109370133B (en) | 2018-10-10 | 2018-10-10 | Method for reinforcing polymethyl methacrylate by cellulose |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111300583A (en) * | 2020-02-28 | 2020-06-19 | 南通大学 | Method for manufacturing wooden light-emitting lampshade |
| CN112078217A (en) * | 2020-09-02 | 2020-12-15 | 中国林业科学研究院林业新技术研究所 | Preparation method of wood reinforced thermoplastic resin-based environment-friendly formaldehyde-free composite material |
| CN112080109A (en) * | 2020-09-02 | 2020-12-15 | 中国林业科学研究院林业新技术研究所 | Preparation method of multidimensional special-shaped high-transparency high-scattering environment-friendly formaldehyde-free wood-based composite material |
| CN112574577A (en) * | 2020-12-14 | 2021-03-30 | 湖南福森竹木科技有限公司 | Nano PVA material wood veneer and preparation method thereof |
| CN114685976A (en) * | 2022-04-27 | 2022-07-01 | 苏州博利迈新材料科技有限公司 | High-toughness conductive nylon material and preparation method thereof |
| CN115075042A (en) * | 2022-07-12 | 2022-09-20 | 大湾区大学(筹) | Lignocellulose-based transparent plastic substitute product, manufacturing method and production system thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111300583A (en) * | 2020-02-28 | 2020-06-19 | 南通大学 | Method for manufacturing wooden light-emitting lampshade |
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| CN114685976A (en) * | 2022-04-27 | 2022-07-01 | 苏州博利迈新材料科技有限公司 | High-toughness conductive nylon material and preparation method thereof |
| CN114685976B (en) * | 2022-04-27 | 2023-10-24 | 苏州博利迈新材料科技有限公司 | High-toughness conductive nylon material and preparation method thereof |
| CN115075042A (en) * | 2022-07-12 | 2022-09-20 | 大湾区大学(筹) | Lignocellulose-based transparent plastic substitute product, manufacturing method and production system thereof |
| CN115075042B (en) * | 2022-07-12 | 2023-08-15 | 大湾区大学(筹) | Lignocellulose-based transparent plastic substitute product, manufacturing method and production system thereof |
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