CN103087516B - Preparation method of nylon 6 and natural fiber composite material - Google Patents
Preparation method of nylon 6 and natural fiber composite material Download PDFInfo
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- CN103087516B CN103087516B CN201310042530.8A CN201310042530A CN103087516B CN 103087516 B CN103087516 B CN 103087516B CN 201310042530 A CN201310042530 A CN 201310042530A CN 103087516 B CN103087516 B CN 103087516B
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Abstract
The invention discloses a preparation method of a nylon 6 and natural fiber composite material. The method comprises the steps that: 1, natural fiber is pretreated; 2, the pretreated natural fiber is dried for 24h in a lyophilization machine; and the fiber is preheated; 3, nylon 6 monomer caprolactam is heated to 80-130 DEG C and is fused; vacuuming dewatering is carried out; an initiator is added, and vacuuming dewatering is carried out; an activating agent is added, the mixture is well mixed, and vacuuming dewatering is carried out, such that an active material is prepared; and 4, the active material is added into natural fiber; rapid vacuuming is carried out; polymerization is carried out for 0.5-1.5h under a polymerization temperature; and cooling is carried out, such that nylon 6 and natural fiber composite material is obtained. According to the material, a reaction processing method is adopted, such that the natural fiber can be more uniformly dispersed in resin, and composite material interface performance can be improved. The mechanical performance of the material is higher than common nylon 6, and the material has an environment-friendly characteristic. The material has a wide application range.
Description
Technical field
The invention belongs to macromolecule material preparation area, be specifically related to the preparation method of a kind of nylon 6 and natural-fiber composite material.
Background technology
Matrix material occupies a tiny space at material science with high strength, the irreplaceable advantage such as energy-conservation, but the discarded of many matrix materials brings day by day serious environmental problem.Along with the continuous enhancing of people's environmental consciousness, the application of renewable, sustainable use and degradable biomaterial receives much attention and payes attention to, and natural fiber as a kind of inexpensive, light weight, specific tenacity and specific rigidity are high, the ep-type material of natural degradation can especially receive the concern of scholar, therefore, the research and development of natural fiber reinforced composite becomes the study hotspot of new millennium, as Chinese patent CN102532661A, CN101003667A, CN102002859A, individually disclose the preparation method of polyethylene, poly(lactic acid), urethane and natural-fiber composite material.
Nylon 6(PA6) as a kind of engineering plastics, it has excellent mechanical property, has again wear-resisting, oil resistant, solvent resistant, self-lubricating, self-extinguishing, the advantage such as erosion resistance and good processing characteristics.Thus, PA6 and natural-fiber composite material have very large application potential quality.But the melt processing temperature of nylon 6 is generally at 230 to 250 DEG C, and the performance of natural fiber can produce serious decline at this temperature, thus the preparation of this traditional forming method to natural fiber and nylon 6 composite material is infeasible.
The reacting processing of nylon 6 composite material with anionic polymerization nylon 6 for matrix, be under basic metal initiator and activator co-catalysis, at 150 DEG C to 180 DEG C polymerase 10 .5 to 1.5h, transformation efficiency is up to more than 95%, molecular weight is 8 to 10 ten thousand, and degree of crystallinity can reach more than 45%.Compared with common hydrolysis nylon 6, anionic polymerization nylon 6 has that polymerization temperature is low, speed of reaction is fast, transformation efficiency is high, intensity and the high feature of Young's modulus.So, as adopted anionic polymerization nylon 6 and natural fiber to carry out reacting processing, then high temperature can be avoided the disadvantageous effect of natural fiber performance, and high performance natural-fiber composite material can be obtained.
Regrettably, so far, the research in natural fiber and nylon 6 reacting processing not yet has report.May be because anionoid polymerization is very harsh to the requirement of synthetic environment, be easy in reaction process be inhibited by proton class impurity.And the main component of natural fiber is Mierocrystalline cellulose, each other with β-1 by many D-Glucopyranose acid anhydrides, the linear macromolecule that 4 glycosidic bonds are formed by connecting, all contain 3 high reactivity hydroxyls in each basic ring in the repeating unit of cellulosic molecule, these hydroxyls be easy to be oxidized, esterification, etherificate, the reaction such as graft copolymerization.So can there is many physical and chemical reactions in natural fiber and anionic polymerization nylon 6 reaction process, these reactions may hinder the carrying out of anionoid polymerization.Therefore, the polymerization system of traditional anionic polymerization nylon 6 is also the reacting processing that can not be directly used in natural-fiber composite material.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of nylon 6 and natural-fiber composite material.
A preparation method for nylon 6 and natural-fiber composite material, comprises the steps:
Step one, pre-treatment is carried out to natural fiber, remove the colloid, grease, PVA, the ash impurities that wherein contain; Sodium hydroxide, Sodium dodecylbenzene sulfonate and sodium carbonate are dissolved in deionized water for stirring by the amount of 3g/L, 3% weight percent and 2% weight percent respectively even, then natural fiber is added by the weight ratio of 1:50, be warmed up to 90 to 100 DEG C, under agitation process 3 to 5h;
Step 2, pretreated natural fiber is placed in temperature is-45 DEG C, dry 24h in the freeze drier of vacuum tightness 9Pa, then preheating under 140 to 180 DEG C and vacuum condition-0.03 to-0.09MPa;
Step 3, nylon 6 monomer hexanolactam is warming up to 80 to 130 DEG C, vacuumize draining 10 to 20min after melting, then add initiator and vacuumize draining 10 to 20min, finally adding activator again, draining 5 to 20min is vacuumized again, obtained active material after mixing;
Step 4, active material step 3 prepared join in natural fiber, and the weight of natural fiber is 1% to 200% of active material weight; Be evacuated to-0.03 to-0.09MPa rapidly, at polymerization temperature 140 to 180 DEG C, polymerase 10 .5 to 1.5h, after cooling, namely obtains nylon 6 and natural-fiber composite material.
Further scheme is: described initiator is hexanolactam magnesium bromide, and add-on is 0.3 to the 2.4mol% of nylon 6 monomer hexanolactam.
Further scheme is: described activator is HDI, TDI, MDI; Diphenyl carbonate, dimethyl terephthalate (DMT); One or more in N-vinylcaprolactam, aminocaproic lactam, two acylated lactams-1,6-hexanediamine, add-on is 0.3 to the 2.4mol% of monomer.
Further scheme is: described natural fiber is one or more in xylon, flaxen fiber, cotton fibre, bamboo fibers, vine fiber ti, straw fiber, wheat straw, straw, rice husk, Caulis Sacchari sinensis fiber, coir, Pericarppium arachidis hypogaeae and pure cellulose, modified-cellulose.
Further scheme is: at least one in the macrofiber that the form of described natural fiber is selected from Fibre diameter is less than the nanofiber of 100nm, length is 0.2 ~ 10mm staple fibre, length is 10 ~ 50mm, continuous fibre.
Further scheme is: described continuous fibre is fabric fibre, fibrefelt or dimensional fibre.
The present invention compared with prior art, has following positively effect:
1, the initiator that anionic polymerization nylon 6 adopts is generally high alkalinity and the high reactivity initiators such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium ethylate, potassium ethylate, hexanolactam sodium salt, hexanolactam sylvite, but they are when participating in natural fiber reacting processing, be easy to react between fiber and be consumed, thus produce inhibition; And the initiator hexanolactam magnesium bromide that the present invention adopts, because it has low activity and weakly alkaline, so by the reaction of the reactionlessness restriction of self with natural fiber, thus the process of natural-fiber composite material reacting processing can be improved;
2, adopt the method for reacting processing to prepare natural-fiber composite material, fiber dispersion effect in more low viscous liquid is better, is conducive to the homogeneity improving end article;
3, the method for reacting processing is adopted to prepare natural-fiber composite material, the interface performance between fiber and matrix can be made to obtain good improvement, and have an opportunity to make to form chemical bonding effect between surface of natural fibers group and matrix, effectively raise composite material combination property;
4, the present invention had first carried out pre-treatment to it before application natural fiber, can remove residual colloid, grease, PVA, ash grade and to have a negative impact impurity to reacting processing, be conducive to carrying out smoothly of reacting processing;
5, the present invention is to pretreated natural fiber, is dewatered to it by freeze drier, because the drying principles of Freeze Drying Equipment is first frozen into by hydrous matter solid-state, then makes moisture content wherein become gaseous state from solid state sublimation, thus removing moisture content and preserve material; Water removes with form of ice crystals, so the free-water of the overwhelming majority can both be gone out.Therefore the drying effect of freeze drier to natural fiber is better than heated drying;
6, all in all, few in the research and development and production of natural-fiber composite material product at present, the invention provides a kind of preparation method of natural-fiber composite material, natural fiber can be made to be more widely used at polymeric material field, what improve natural fiber utilizes level, can stimulate the development of China's natural fiber industry simultaneously.
Embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art in this field makes the present invention according to the invention described above content and adjustment still belong to protection scope of the present invention.
Embodiment 1
Caprolactam monomer is joined in reactor; draining 15min is vacuumized after being warming up to 100 DEG C of meltings; then add initiator hexanolactam magnesium bromide 0.6mol% and vacuumize draining 15min; finally add two acylated lactams-1 again; 6-hexanediamine 0.6mol%, vacuumizes 10min after mixing again.Being poured into by the above-mentioned active material prepared is placed with in the mould of ramie fabric, is evacuated to-0.05Mpa rapidly, is polymerized 60min, after mould naturally cooling, obtains composite product at polymerization temperature 160 DEG C.
Embodiment 2
Caprolactam monomer is joined in reactor, after being warming up to 120 DEG C of meltings, vacuumize draining 15min, then add initiator hexanolactam magnesium bromide 0.6mol% and vacuumize draining 15min, finally adding TDI 0.6mol% again, mix.Being poured into by the above-mentioned active material prepared is placed with in the mould of ramie fabric, is evacuated to-0.05Mpa rapidly, is polymerized 60min, after mould naturally cooling, obtains composite product at polymerization temperature 165 DEG C.
Embodiment 3
Caprolactam monomer is joined in reactor; draining 15min is vacuumized after being warming up to 100 DEG C of meltings; then add initiator hexanolactam magnesium bromide 0.6mol% and vacuumize draining 15min; subsequently dried cellulose powder 5% is joined in solution; abundant stirring makes it dispersed; finally add two acylated lactams-1,6-hexanediamine 0.6mol% again, after mixing, vacuumize 10min again.The above-mentioned active material prepared is poured in the mould of preheating, is evacuated to-0.096Mpa rapidly, at polymerization temperature 160 DEG C, be polymerized 60min, after mould naturally cooling, obtain composite product.
Embodiment 4
Caprolactam monomer is joined in reactor; draining 15min is vacuumized after being warming up to 100 DEG C of meltings; then add initiator hexanolactam magnesium bromide 0.6mol% and vacuumize draining 15min; subsequently dried ramie chopped strand 5% is joined in solution; abundant stirring makes it dispersed; finally add two acylated lactams-1,6-hexanediamine 0.6mol% again, after mixing, vacuumize 10min again.The above-mentioned active material prepared is poured in the mould of preheating, is evacuated to-0.096Mpa rapidly, at polymerization temperature 160 DEG C, be polymerized 60min, after mould naturally cooling, obtain composite product.
Embodiment 5
Caprolactam monomer is joined in reactor; draining 15min is vacuumized after being warming up to 100 DEG C of meltings; then add initiator hexanolactam magnesium bromide 0.6mol% and vacuumize draining 15min; finally add two acylated lactams-1 again; 6-hexanediamine 0.6mol%, vacuumizes 10min after mixing again.Being imported under vacuum by the above-mentioned active material prepared is placed with in the closed mould of ramie fabric, and vacuum tightness is-0.05MPa, is polymerized 60min, after mould naturally cooling, obtains composite product at polymerization temperature 160 DEG C.Its performance testing index is as shown in table 1.
The performance test table of table 1 natural fiber and nylon 6 in-situ matrix material
| Transformation efficiency % | Fibre content/wt% | Degree of crystallinity/% | Fusing point/DEG C | Modulus in flexure/MPa |
| 94.1 | 37 | 56 | 220 | 3407 |
Claims (5)
1. a preparation method for nylon 6 and natural-fiber composite material, is characterized in that comprising the steps:
Step one, pre-treatment is carried out to natural fiber, remove the colloid, grease, PVA, the ash impurities that wherein contain; Sodium hydroxide, Sodium dodecylbenzene sulfonate and sodium carbonate are dissolved in deionized water for stirring by the amount of 3g/L, 3% weight percent and 2% weight percent respectively even, then natural fiber is added by the weight ratio of 1:50, be warmed up to 90 to 100 DEG C, under agitation process 3 to 5h;
Step 2, pretreated natural fiber is placed in dry 24h, then preheating under 140 to 180 DEG C and vacuum condition-0.03 to-0.09MPa in freeze drier that temperature is-45 C, vacuum tightness 9Pa;
Step 3, nylon 6 monomer hexanolactam is warming up to 80 to 130 DEG C, vacuumize draining 10 to 20min after melting, then add initiator and vacuumize draining 10 to 20min, finally adding activator again, draining 5 to 20min is vacuumized again, obtained active material after mixing;
Step 4, active material step 3 prepared join in natural fiber, and the weight of natural fiber is 1% to 200% of active material weight; Be evacuated to-0.03 to-0.09MPa rapidly, at polymerization temperature 140 to 180 DEG C, polymerase 10 .5 to 1.5h, after cooling, namely obtains nylon 6 and natural-fiber composite material;
Described activator is HDI, TDI, MDI; Diphenyl carbonate, dimethyl terephthalate (DMT); One or more in N-vinylcaprolactam, aminocaproic lactam, two acylated lactams-1,6-hexanediamine, add-on is 0.3 to the 2.4mol% of monomer.
2. the preparation method of nylon 6 and natural-fiber composite material according to claim 1, it is characterized in that: described initiator is hexanolactam magnesium bromide, add-on is 0.3 to the 2.4mol% of nylon 6 monomer hexanolactam.
3. the preparation method of nylon 6 and natural-fiber composite material according to the arbitrary claim of claim 1 to 2, is characterized in that: described natural fiber is one or more in xylon, flaxen fiber, cotton fibre, bamboo fibers, vine fiber ti, straw fiber, wheat straw, straw, rice husk, Caulis Sacchari sinensis fiber, coir, Pericarppium arachidis hypogaeae and pure cellulose, modified-cellulose.
4. the preparation method of nylon 6 and natural-fiber composite material according to claim 3, is characterized in that: at least one in the macrofiber that the form of described natural fiber is selected from Fibre diameter is less than the nanofiber of 100nm, length is 0.2 ~ 10mm staple fibre, length is 10 ~ 50mm, continuous fibre.
5. the preparation method of nylon 6 and natural-fiber composite material according to claim 4, is characterized in that: described continuous fibre is fabric fibre, fibrefelt or dimensional fibre.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103421184B (en) * | 2013-08-05 | 2015-07-22 | 福建景丰科技有限公司 | Method for preparing chinlon 6 slices |
| CN103923522B (en) * | 2014-04-03 | 2016-05-04 | 东华大学 | A kind of for rapid three dimensional printing forming nylon 6 inks and application thereof |
| CN104313876B (en) * | 2014-10-15 | 2017-01-18 | 四川大学 | Method for modifying natural fibers for anion polymer nylon 6 reaction |
| CN104774450A (en) * | 2015-04-22 | 2015-07-15 | 合肥康龄养生科技有限公司 | Novel antimicrobial nylon composite material and preparation method thereof |
| CN105885396B (en) * | 2016-05-11 | 2018-06-22 | 湖南大学 | A kind of natural ramie fiber enhancing cast composite nylon material and preparation method thereof |
| CN109830335A (en) * | 2019-03-29 | 2019-05-31 | 安徽徽宁电器仪表集团有限公司 | A kind of tensile type shielded cable |
| CN110452530A (en) * | 2019-08-16 | 2019-11-15 | 东莞市众一新材料科技有限公司 | A kind of natural fiber reinforcement biology base nylon material and preparation method thereof |
| CN110713712A (en) * | 2019-11-22 | 2020-01-21 | 安徽微威减震降噪技术研究院 | Copolymerization modified polyamide material and preparation method thereof |
| CN113670005B (en) * | 2021-09-03 | 2022-06-21 | 海西纺织新材料工业技术晋江研究院 | Drying method of polyglycolide warp-knitted supporting net for artificial skin |
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| KR101855544B1 (en) * | 2010-10-07 | 2018-05-04 | 바스프 에스이 | Method for producing monomer compositions, and use thereof for producing a molded polyamide part |
| CN102153744B (en) * | 2011-02-23 | 2013-01-23 | 株洲时代新材料科技股份有限公司 | Preparation method of halloysite nanotube reinforced flame-retardant anionic polymerization nylon |
| CN102409328B (en) * | 2011-11-02 | 2013-08-21 | 甘肃蓝科石化高新装备股份有限公司 | Surface modification method of alloy fiber |
| CN102493184B (en) * | 2011-12-12 | 2014-03-26 | 中国科学院宁波材料技术与工程研究所 | Interface-enhanced carbon fiber/polycaprolactam composite material and preparation method thereof |
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