CN105885396A - Natural fibrilia reinforced cast nylon composite material and preparation method thereof - Google Patents
Natural fibrilia reinforced cast nylon composite material and preparation method thereof Download PDFInfo
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- CN105885396A CN105885396A CN201610308930.2A CN201610308930A CN105885396A CN 105885396 A CN105885396 A CN 105885396A CN 201610308930 A CN201610308930 A CN 201610308930A CN 105885396 A CN105885396 A CN 105885396A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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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
- C08L2201/06—Biodegradable
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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
- C08L2205/14—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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
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Abstract
The invention discloses a natural fibrilia reinforced cast nylon composite material and a preparation method thereof. The composite material is formed by in-situ composition of caprolactam and treated natural fibrilia through ring opening polymerization. The preparation method comprises the following steps: carrying out thermal treatment on the natural fibrilia first under an inert atmosphere, cooling and then putting in a mold, heating and melting the caprolactam, adding a catalyst and an activating agent, and uniformly mixing; introducing the mixture to the mold and carrying out ring opening polymerization to obtain the finished product. The method disclosed by the invention realizes organic combination of the natural fibrilia and nylon 6, can be used for obtaining the natural fibrilia reinforced cast nylon composite material with excellent comprehensive performances and is high in efficiency, low in pollution and capable of meeting industrial production and overcoming the technical defect that the existing natural fibrilia and the caprolactam are difficult to composite due to the polymerization inhibition of the existing natural fibrilia to the caprolactam.
Description
Technical field
The present invention relates to a kind of natural ramie fiber and strengthen cast composite nylon material and preparation method thereof；Belong to high score
Sub-field of material technology.
Background technology
Monomer cast nylon is at ambient pressure with alkaline material, melted raw material caprolactam monomer to be made catalyst,
Together with promoter, being directly injected in the mould being preheating to uniform temperature, material is quickly carried out in a mold
Polyreaction, condenses into tough and tensile solid product.Compared with hydrolytic polymerization, anionic ring-opening polymerization has synthesis
The advantages such as the time is short, simple to operate, product size is big, the molecular weight of monomer cast nylon goods is high, degree of crystallinity is big,
Mechanical property is good.Therefore, monomer cast nylon can be widely applied to automobile, instrument and meter, machinery, weaving, chemical industry
Parts and structural member in field.
Compared with glass fiber reinforcement cast composite nylon material, natural fiber strengthens cast composite nylon material more
Add environmental protection, the discharge of pollutant can be reduced, degradable, moreover it is possible to reduce the consumption of energy.Additionally, natural fiber
The most cheap, wide material sources, renewable, density is low, and specific strength advantages of higher, in recent years due to oil
Crisis is more exposed to favor.But flaxen fiber be mainly composed of cellulose, containing big in cellulose molecular structure
The hydroxyl of amount；And flaxen fiber surface polarity is relatively big, shows strong hydrophilic, from air, easily absorb water
Part, cause flaxen fiber to strengthen in cast composite nylon material preparation process and occur that serious inhibition phenomenon can not be gathered
Close.This is complicated mainly due to surface of natural fibers group, and the condition of anionic polymerisation is the harshest, holds
It is vulnerable to external influence.
Chen Peng etc. [Chen Peng etc., polymer material science and engineering, 2014] use vacuum-assisted resin transfer mould
(VARTM) method of moulding is prepared for natural fiber and strengthens anionic polymerization nylon 6 composite.Result shows, right
Natural fiber is carried out after solution remove impurity pretreatment in 80 DEG C of vacuum drying, have chosen low activity and weakly alkaline oneself
Lactams magnesium bromide is as initiator, and double acylated lactams-1,6-hexamethylene diamine is activator, prepares natural fibre
Dimension composite.But owing to composite preparation process employing price initiator costly and activation
Agent, is unfavorable for that industrialized production and natural fiber strengthen promoting the use of of anionic polymerization nylon 6 composite.
But the most do not report about preparing flaxen fiber enhancing cast composite nylon material after flaxen fiber heat treatment.
Summary of the invention
Substantial amounts of hydroxyl is contained and owing to flaxen fiber surface is highly polar for natural ramie fiber of the prior art
And easily absorb water, cause natural ramie fiber to strengthen in cast composite nylon material preparation process and serious inhibition occurs
And can not be polymerized, it is an object of the invention to provide a kind of natural ramie fiber organically combines with nylon, combination property
Excellent natural ramie fiber strengthens cast composite nylon material.
Further object is that offer one realizes obtain compound with nylon perfection of natural ramie fiber and combines
Closing the method that the natural ramie fiber of excellent performance strengthens cast composite nylon material, the method efficiency is high, it is low to pollute,
Meet industrialized production, and overcome existing natural ramie fiber and make both be difficult to be combined caprolactam inhibition
Technological deficiency.
The invention discloses a kind of natural ramie fiber and strengthen cast composite nylon material, this composite is by acyl in oneself
Amine is formed by the natural ramie fiber In-situ reaction that ring-opening polymerisation is heat treated with 180～400 DEG C.
Under normal conditions, owing to substantial amounts of active group is contained on natural ramie fiber surface, caprolactam is gathered
Close and there is inhibition phenomenon, make both be difficult to organically combine.Technical scheme, by natural ramie fiber
Carry out heat treatment (180～400 DEG C) and can not only fully remove physical bond water, but also surface can be removed
Hydroxyl and other impurity, meanwhile, the natural ramie fiber of heat treatment still has preferable mechanics at such a temperature
Performance.Due to the abundant removing of flaxen fiber surface active groups, significantly reduce polarity matrix to anionic polymerisation
Interference, strengthen at flaxen fiber and inhibit phenomenon during cast composite nylon material and substantially disappear, it is possible to obtain combine
The natural ramie fiber closing excellent performance strengthens cast composite nylon material.
Preferably scheme, natural ramie fiber is 10～45%:55～90% with the mass percent of caprolactam.
More preferably scheme, natural ramie fiber is thickness natural ramie fiber cloth or natural in the range of 0.1～3mm
Bast fibre felt, wherein, monofilament flaxen fiber a diameter of 10～30 μm.
Further preferred scheme, natural ramie fiber be tossa cloth, ramie fibre cloth, flax fiber cloth,
At least one in gombo hemp fiber cloth, jute felt, ramee felt, flaxfiber nonwoven, gombo hemp fiber felt.
Preferably scheme, ring-opening polymerisation adds catalyst and activator.It is 100 parts of meterings with quality of caprolactam,
Catalyst is 0.1～1.5 part relative to the addition of caprolactam, and activator relative to the addition of caprolactam is
0.1～1.5 part.
More preferably scheme, catalyst be sodium hydroxide, potassium hydroxide, Feldalat NM, sodium caprolactam at least
A kind of.The catalyst that the present invention uses can be conventional, cheap alkali, overcomes and uses costliness in prior art
Caprolactam magnesium bromide as the defect of initiator.
Preferably scheme, activator is hexamethylene diisocyanate, toluene di-isocyanate(TDI), tritan. three
At least one in isocyanates.
Present invention also offers described natural ramie fiber and strengthen the preparation method of cast composite nylon material, the party
Method comprises the following steps:
(1) heat treatment is carried out at a temperature of under an inert atmosphere, natural ramie fiber being placed in 180～400 DEG C；
(2), after caprolactam being added heat fusing, catalyst and activator mix homogeneously are added；
(3) (2) gained mixed material vacuum is imported it is filled with through (1) heat treated natural ramie fiber
Mould in, at a temperature of 120～170 DEG C, carry out ring-opening polymerization, to obtain final product.
Preferably scheme, heat treatment time is 5～30min.
Preferably scheme, the ring-opening polymerization time is 10～30min.
Preferably scheme, heat treatment temperature is 180～300 DEG C.
The present invention prepares the method that natural ramie fiber strengthens cast composite nylon material, comprises the following steps:
(1) first according to the size of mould, natural fiber cloth or felt are carried out cutting；Natural ramie fiber cloth or felt
Under the conditions of heat treatment is inert gas shielding, with the heating rate of 5～10 DEG C/min, from room temperature to 180～400
DEG C, and it is incubated 5～30min, and it being cooled to room temperature, vacuum saves backup；
(2) again natural fiber cloth complete for heat treatment or felt are stacked into suitable thickness to be positioned in mould,
Sealed mold, is warming up to 120～170 DEG C；Caprolactam is added in the container of band stirring, be warming up to 120～170
DEG C, vacuum dehydration 20～40min；Again catalyst is added, vacuum dehydration under the conditions of 120～170 DEG C
15～20min；Add activator and stir；
(3) with vacuum pump by quick for aforesaid liquid suction mould, termination of pumping after liquid fully infiltrates mould, protect
Temperature 10～30min, die sinking i.e. obtains described natural ramie fiber and strengthens cast composite nylon material.
Hinge structure, the beneficial effect that technical scheme is brought:
1, the natural ramie fiber enhancing cast composite nylon material cheaper starting materials of the present invention, abundance, significantly
Reduce the cost of composite, and reinforcing fiber be Biodegradable material, can with complete biodegradable,
Environmentally friendly；Compared with monomer cast nylon, the cast composite nylon material strengthened by flaxen fiber comprehensive
Can be excellent, intensity dramatically increases, and particularly bending modulus has the raising of 3～4 times；The composite property of preparation
Reach the requirement of high performance engineering plastics, can be widely applied to automobile, instrument and meter, machinery, weave, change
The fields such as work；
2, the preparation method of the present invention is simple, and equipment requirements is low, production process environmental protection, is conducive to industry metaplasia
Produce.
Accompanying drawing explanation
[Fig. 1] is embodiment 4 ramee felt picture；
[Fig. 2] is that embodiment 4 is in 270 DEG C of heat treatment ramee felt pictures；
[Fig. 3] is that embodiment 4 natural remie fiber felt strengthens cast composite nylon material picture.
Detailed description of the invention
Following example are that the present invention further illustrates rather than limits the protection model of the claims in the present invention
Enclose.
The raw material sources of the present invention: caprolactam (can directly be purchased from Sinopec Group's bar
Mound branch company), sodium hydroxide (can directly be purchased from Tianjin Jin Feng Chemical Co., Ltd.), Feldalat NM (can be direct
Be purchased from Shanghai Yi Zha Industrial Co., Ltd.), hexamethylene diisocyanate (can directly be purchased from the brilliant pure biochemistry in Shanghai
Science and Technology Co., Ltd.), toluene di-isocyanate(TDI) (can directly be purchased from West Asia, Shandong chemical industry company limited),
Jute felt (can directly be purchased from Jiangxi Si Chuanma industry company limited), ramee felt (can directly be purchased from mountain
East extensive and profound in meaning Environmental Protection Technology Co., Ltd), tossa cloth and ramie fibre cloth (limited by Hunan canary fiber crops industry
Company provides)
Embodiment 1:
Being arranged in vacuum carbonized stove by the tossa cut, logical nitrogen protection, with the intensification of 10 DEG C/min
Speed, from room temperature to 220 DEG C, and is incubated 10min, is cooled to room temperature, and vacuum saves backup；Again by upper
State the complete tossa cloth of heat treatment and stack into suitable thickness, weigh 35 parts and be placed in mould, sealed mold,
It is warming up to 130 DEG C；200 parts of caprolactams are added in the there-necked flask of band magnetic agitation, be warming up to 130 DEG C, very
Empty dehydration 30min；0.4 part of NaOH will be added again, vacuum dehydration 15min under the conditions of 130 DEG C；Add 0.5 part
TDI also stirs；With vacuum pump by quick for aforesaid liquid suction mould, stop after liquid fully infiltrates mould
Pump, is incubated 30min, and die sinking i.e. obtains described natural tossa cloth and strengthens cast composite nylon material.
Embodiment 2:
Being arranged in vacuum carbonized stove by the ramee cut, logical nitrogen protection, with the intensification of 10 DEG C/min
Speed, from room temperature to 270 DEG C, and is incubated 10min, is cooled to room temperature, and vacuum saves backup；Again by upper
State the complete ramie fibre cloth of heat treatment and stack into suitable thickness, weigh 35 parts and be placed in mould, sealed mold,
It is warming up to 130 DEG C；200 parts of caprolactams are added in the there-necked flask of band magnetic agitation, be warming up to 130 DEG C, very
Empty dehydration 30min；0.4 part of NaOH will be added again, vacuum dehydration 15min under the conditions of 130 DEG C；Add 0.4 part
TDI also stirs；With vacuum pump by quick for aforesaid liquid suction mould, stop after liquid fully infiltrates mould
Pump, is incubated 30min, and die sinking i.e. obtains described natural remie fiber cloth and strengthens cast composite nylon material.
Embodiment 3:
Being placed in vacuum carbonized stove by the jute felt cut, logical nitrogen protection, with the intensification of 10 DEG C/min
Speed, from room temperature to 220 DEG C, and is incubated 10min, is cooled to room temperature, and vacuum saves backup；Again by upper
State the complete jute felt of heat treatment and stack into suitable thickness, weigh 30 parts and be placed in mould, sealed mold,
It is warming up to 140 DEG C；200 parts of caprolactams are added in the there-necked flask of band magnetic agitation, be warming up to 140 DEG C, very
Empty dehydration 30min；0.4 part of NaOH will be added again, vacuum dehydration 15min under the conditions of 140 DEG C；Add 0.5 part
TDI also stirs；With vacuum pump by quick for aforesaid liquid suction mould, stop after liquid fully infiltrates mould
Pump, is incubated 30min, and die sinking i.e. obtains described natural jute felt and strengthens cast composite nylon material.
Embodiment 4:
Being placed in vacuum carbonized stove by the ramee felt cut, logical nitrogen protection, with the intensification of 10 DEG C/min
Speed, from room temperature to 270 DEG C, and is incubated 10min, is cooled to room temperature, and vacuum saves backup；Again by upper
State the complete ramee felt of heat treatment and stack into suitable thickness, weigh 30 parts and be placed in mould, sealed mold,
It is warming up to 140 DEG C；200 parts of caprolactams are added in the there-necked flask of band magnetic agitation, be warming up to 140 DEG C, very
Empty dehydration 30min；0.4 part of NaOH will be added again, vacuum dehydration 15min under the conditions of 140 DEG C；Add 0.4 part
TDI also stirs；With vacuum pump by quick for aforesaid liquid suction mould, stop after liquid fully infiltrates mould
Pump, is incubated 30min, and die sinking i.e. obtains described natural remie fiber felt and strengthens cast composite nylon material.
Comparative example 1
200 parts of caprolactams are added in the there-necked flask of band magnetic agitation, be warming up to 140 DEG C, vacuum dehydration
30min；0.4 part of NaOH will be added again, vacuum dehydration 15min under the conditions of 140 DEG C；Add 0.4 part of TDI also
Stir；With vacuum pump by quick for aforesaid liquid suction mould, being incubated 30min, die sinking i.e. obtains described casting mold
Nylon.
Wherein embodiment 1～4 and comparative example 1 prepared by natural ramie fiber strengthen cast composite nylon material
Tensile property according to GB/T 1447-2005, bending property according to GB/T 1449-2005, impact strength according to
GB/T 1451-2005 detects, and its performance parameter is as shown in table 1.
Table 1 natural ramie fiber strengthens the performance of cast composite nylon material
Claims (10)
1. a natural ramie fiber strengthens cast composite nylon material, it is characterised in that: passed through open loop by caprolactam
It is polymerized the natural ramie fiber In-situ reaction heat treated with 180～400 DEG C to form.
Natural ramie fiber the most according to claim 1 strengthens cast composite nylon material, it is characterised in that: described
The mass percent of natural ramie fiber and caprolactam be 10～45%:55～90%.
Natural ramie fiber the most according to claim 1 strengthens cast composite nylon material, it is characterised in that: described
Natural ramie fiber be thickness natural ramie fiber cloth in the range of 0.1～3mm or natural ramie fiber felt, wherein,
Monofilament flaxen fiber a diameter of 10～30 μm.
Natural ramie fiber the most according to claim 3 strengthens cast composite nylon material, it is characterised in that: described
Natural ramie fiber be tossa cloth, ramie fibre cloth, flax fiber cloth, gombo hemp fiber cloth, tossa
At least one in felt, ramee felt, flaxfiber nonwoven, gombo hemp fiber felt.
5. strengthening cast composite nylon material according to the natural ramie fiber described in any one of Claims 1 to 4, its feature exists
In: described ring-opening polymerisation adds catalyst and activator.
Natural ramie fiber the most according to claim 5 strengthens cast composite nylon material, it is characterised in that: described
Catalyst be at least one in sodium hydroxide, potassium hydroxide, Feldalat NM, sodium caprolactam.
Natural ramie fiber the most according to claim 5 strengthens cast composite nylon material, it is characterised in that: described
Activator be in hexamethylene diisocyanate, toluene di-isocyanate(TDI), triphenylmethane triisocyanate extremely
Few one.
8. the natural ramie fiber described in claim 5 strengthens the preparation method of cast composite nylon material, it is characterised in that:
Comprise the following steps:
(1) heat treatment is carried out at a temperature of under an inert atmosphere, natural ramie fiber being placed in 180～400 DEG C；
(2), after caprolactam being added heat fusing, catalyst and activator mix homogeneously are added；
(3) (2) gained mixed material vacuum is imported it is filled with through (1) heat treated natural ramie fiber
Mould in, at a temperature of 120～170 DEG C, carry out ring-opening polymerization, to obtain final product.
Natural ramie fiber the most according to claim 8 strengthens the preparation method of cast composite nylon material, its feature
It is: heat treatment time is 5～30min.
Natural ramie fiber the most according to claim 8 strengthens the preparation method of cast composite nylon material, and it is special
Levy and be: the ring-opening polymerization time is 10～30min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610308930.2A CN105885396B (en) | 2016-05-11 | 2016-05-11 | A kind of natural ramie fiber enhancing cast composite nylon material and preparation method thereof |
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| CN201610308930.2A CN105885396B (en) | 2016-05-11 | 2016-05-11 | A kind of natural ramie fiber enhancing cast composite nylon material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383364A (en) * | 2017-07-27 | 2017-11-24 | 株洲时代新材料科技股份有限公司 | A kind of protection means for automobile material and its preparation technology |
| CN107603209A (en) * | 2017-09-21 | 2018-01-19 | 湖南大学 | A kind of preparation method of acetylated modification string reinforced nylon 6 composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1869107A (en) * | 2006-06-20 | 2006-11-29 | 东华大学 | Preparation method of reinforced polylactic acid composite material for ramie-fabric |
| CN103087516A (en) * | 2013-02-04 | 2013-05-08 | 四川大学 | Preparation method of nylon 6 and natural fiber composite material |
| CN104313876A (en) * | 2014-10-15 | 2015-01-28 | 四川大学 | Method for modifying natural fibers for anion polymer nylon 6 reaction |
-
2016
- 2016-05-11 CN CN201610308930.2A patent/CN105885396B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1869107A (en) * | 2006-06-20 | 2006-11-29 | 东华大学 | Preparation method of reinforced polylactic acid composite material for ramie-fabric |
| CN103087516A (en) * | 2013-02-04 | 2013-05-08 | 四川大学 | Preparation method of nylon 6 and natural fiber composite material |
| CN104313876A (en) * | 2014-10-15 | 2015-01-28 | 四川大学 | Method for modifying natural fibers for anion polymer nylon 6 reaction |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383364A (en) * | 2017-07-27 | 2017-11-24 | 株洲时代新材料科技股份有限公司 | A kind of protection means for automobile material and its preparation technology |
| CN107603209A (en) * | 2017-09-21 | 2018-01-19 | 湖南大学 | A kind of preparation method of acetylated modification string reinforced nylon 6 composite |
| CN107603209B (en) * | 2017-09-21 | 2019-10-22 | 湖南大学 | A kind of preparation method of acetylated modification plant fiber reinforced nylon 6 composite material |
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