CN100560643C - Flexible controlled in-situ micro-fibril matrix material of fento and preparation method thereof - Google Patents
Flexible controlled in-situ micro-fibril matrix material of fento and preparation method thereof Download PDFInfo
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- CN100560643C CN100560643C CNB2006100218280A CN200610021828A CN100560643C CN 100560643 C CN100560643 C CN 100560643C CN B2006100218280 A CNB2006100218280 A CN B2006100218280A CN 200610021828 A CN200610021828 A CN 200610021828A CN 100560643 C CN100560643 C CN 100560643C
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Abstract
The invention discloses the preparation method of polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene (or polypropylene) in-situ micro-fibril matrix material, this method is earlier with polyethylene terephthalate and polyester thermoplastic elastomer blending, again with this blend with after polyethylene (or polypropylene) mixes according to certain proportioning, through " melt extruding-thermal stretch-quenching " process, last granulation makes the in-situ micro-fibril matrix material.In this material, polyethylene terephthalate/polyester thermoplastic elastomer blend is fibrous.Elastomeric content increases the snappiness of fento in the fento by increasing, thereby improves the processing fluidity of in-situ micro-fibril matrix material and reduce melt elasticity.
Description
One, technical field
The invention belongs to the novel high polymer material technical field, relate to a kind of novel in-situ micro-fibril matrix material and preparation method thereof.
Two, background technology
It is to improve the mechanics of general-purpose plastics and the effective ways of resistance toheat that general-purpose plastics (mainly referring to polyolefine) and general engineering plastic (as polyethylene terephthalate, polymeric amide and polycarbonate etc.) are carried out blend.In most cases, general-purpose plastics/engineering plastics blend is incompatible on thermodynamics, disperse phase forms different morphological structures in the course of processing, as spherical, ellipsoid shape, bar-shaped, fento shape, plate-like, equate form continuously altogether, and the character of blend depends on the form of disperse phase to a great extent.Therefore make disperse phase original position in matrix form fiber by special method for processing forming, become the important channel of improving the general-purpose plastics performance thereby reach the enhancing purpose.Because fortifying fibre original position (in-situ) in the course of processing generates, and fiber is compared with macroscopic fiber, and small-sized (general diameter is less than 10 μ m, length-to-diameter ratio is greater than hundreds of), so the blend material that this method is obtained be defined as " in-situ micro-fibril matrix material " (in-situ microfibrillarreinforced composite, MRC).The in-situ micro-fibril matrix material with the thermotropic liquid crystal be fento mutually, thermoplastic polymer is liquid crystal in-situ composite (the Kiss G.Polym Eng Sci of matrix, 1987,27:410) compare, because thermoplastic polymer fento phase material wide material sources, moderate, processing forming is good, little to equipment attrition, processing temperature is low, therefore, thermoplastic polymer has obtained increasing attention as the fibrous composite with micro of fento phase.Because fento and matrix all are thermoplastic polymers in the fibrous composite with micro, also such fibrous composite with micro are called thermoplastic polymer/thermoplastic polymer in-situ micro-fibril matrix material.
Thermoplastic polymer/thermoplastic polymer in-situ composite and thermoplastic polymer that have obvious processing temperature difference incompatible by two kinds formed, and the component that has than high processing temperature forms fento in the course of processing.At present, prepare this in-situ micro-fibril matrix material and mainly adopt following two kinds of methods:
(1) two kinds of thermoplastic polymer blend is extruded, cooling off solid phase stretches, between two component fusing points, anneal then, make molecular chain disorientation as the low-melting component of matrix, maintenance is as the phase structure of the orientation of the high melting point component of disperse phase, and this is called " melt extruding-solid phase stretching-anneal " method (Fakirov S, et al.Macromolecules, 1993,26:5219).
(2) when blend is extruded, before extrudate is uncolled, melt is carried out thermal stretch, make high melting point component form fiber form as disperse phase, and quenching keeps this form get off, this be called " melt extruding-thermal stretch-quenching " method (Li Zhongming etc., Chinese patent, CN01128896.5).
The temperature that the fibrous composite with micro that adopts two kinds of methods to obtain is reprocessed is between two kinds of component processing temperatures, because processing temperature is lower than the fusing point of the disperse phase that is fiber, so contain the enhanced fiber in the final material.Adopt in " melt extruding-solid phase stretching-anneal ", the process complexity, efficient is low, only can do theoretical investigation.And when adopting the method for " melt extruding-thermal stretch-quenching ", do not need reheat to carry out solid phase and stretch and aftertreatment, technology is continuous, is easy to control and simple relatively, and the production efficiency height obtains practical application easily.
Prior art has prepared various engineering plastics (polyethylene terephthalate, polycarbonate, polymeric amide)/polyolefine (polyethylene, polypropylene) in-situ micro-fibril matrix material, and find the purer polyolefine material of mechanical property of thermoplastic polymer/thermoplastic polymer in-situ micro-fibril matrix material and the common matrix material of tensile (Li Zhongming etc. that are significantly improved not, Chinese patent, CN01128896.5; Li ZM, et al.Mater Lett, 2002.56:756).During with in-situ micro-fibril Composite Preparation plastics, the working method of article shape (thickness, size etc.), goods is to Drawing abillity, and particularly the viscosity of melt has different requirements with elastic parameter.For example,, require goods to have good mobility, do not reach service requirements otherwise the discontented phenomenon of punch die can occur for thin-walled or large-sized injection-molded item; And for most of extruded products, require the smooth surface of goods smooth, this is just closely related with the elasticity of plastic melt, if the elasticity of melt is bigger, the instability of extruding that under lower extruded velocity, just occurs melt easily, or even the shark skin phenomenon, have a strong impact on surface quality, and reduce extruded velocity production efficiency is reduced.Therefore, to the in-situ micro-fibril matrix material, improve and control its processing characteristics and seem extremely important.Because fento has very little diameter and bigger length-to-diameter ratio in the fibrous composite with micro, tangle mutually easily even the formation network structure, this can increase viscosity and elasticity (Xu Hongsheng etc., Chinese plastics 2006, the 20:18 of Composite Melt to a great extent; Xu HS, et al.Polym Eng Sci, 2005,45:1231), cause its processing fluidity relatively poor.
Three, summary of the invention
The purpose of this invention is to provide the flexible controlled in-situ micro-fibril matrix material of a kind of fento, the elasticity and the sticky parameter of the melt of the soft readjustment fibrous composite with micro by the control fento reach the purpose of improving the fibrous composite with micro processing characteristics.
Another object of the present invention provides a kind of preparation method of above-mentioned in-situ micro-fibril matrix material.
The flexible controlled in-situ micro-fibril matrix material of fento of the present invention, the used starting material of this matrix material are by mass percentage:
Polyethylene terephthalate/polyester thermoplastic elastomer blend 5%～40% (wherein the massfraction of polyethylene terephthalate in blend is 70%～98%)
In polyethylene or the polypropylene a kind of 60%～95%.
In the component of above-mentioned matrix material, polyethylene terephthalate can be commercially available any one, thermoplastic elastomer has been selected the polyester thermoplastic elastomer that better consistency is arranged with polyethylene terephthalate for use, is preferably to have high melt point (general＞200 ℃); Polyethylene can be selected any one the commercially available polyethylene except that ultrahigh molecular weight polyethylene(UHMWPE) for use; Polypropylene can be commercially available any one.
By with polyethylene terephthalate with obtain blend as the fento phase material with its polyester thermoplastic elastomer resin after mixing with better consistency, carry out preparing polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene (or polypropylene) in-situ micro-fibril matrix material after " melt extruding-thermal stretch-quenching " with polyethylene (or polypropylene) again, the fento flexibility can be by increasing the content of polyester thermoplastic elastomer in the fento in the matrix material, under the condition of the form that does not change fento substantially (length-to-diameter ratio and diameter) and be improved.Both can realize the high performance of general-purpose plastics also solving the technics of reclaim of plastic waste problem with in-situ micro-fibril matrix material provided by the invention, when reducing the isolating operation of plastics, reach the enhanced purpose.Can also control the flexibility of fento simultaneously by the content of regulating polyester thermoplastic elastomer component in the fento, finally reach the processing characteristics of regulating matrix material, to adapt to the needs of different processing methods.
The method for preparing the controlled in-situ micro-fibril matrix material of fento flexibility of the present invention is made up of following steps successively:
At first, be that 98%～70% polyethylene terephthalate and 2%～30% polyester thermoplastic elastomer prepare polyethylene terephthalate/polyester thermoplastic elastomer blend by following processing step and condition with massfraction.
(1) dry with above-mentioned pet resin and polyester thermoplastic elastomer in 80～120 ℃ baking oven dry 8～24 hours, control water ratio＜0.01%.
(2) melting mixing earlier with polyethylene terephthalate in airtight mixing machine under 260～295 ℃, the rotating speed of rotor is 10～100 rev/mins, treat after the complete fusion (5～10min), add the polyester thermoplastic elastomer, mixing 10～15 minutes under with 30～100 rev/mins rotating speed under the identical temperature.
(3) granulation is broken in crusher with the polyethylene terephthalate in the mixing machine/polyester thermoplastic elastomer blend, and the preferred particle diameter after the fragmentation is less than the particle of 5mm.
Then, polyethylene terephthalate/polyester thermoplastic elastomer blend and polyethylene (or polypropylene) blend are extruded preparation polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene (or polypropylene) fibrous composite with micro.The main technique step is as follows:
(4) doing mixed polyethylene terephthalate/5～40 parts and 95～60 parts polyethylene of polyester thermoplastic elastomer blend (or polypropylene) are stirred at normal temperatures mixes.
(5) melting mixing, slit mouth mould are extruded and first blended material is placed the forcing machine melting mixing and are extruded, and extrusion temperature is 150～295 ℃, 270～295 ℃ of die temperatures, 10～200 rev/mins of extruder screw rotating speeds.The big I of forcing machine determines that according to turnout basic demand is: length-to-diameter ratio is 20～40; Not additional hybrid element.The mouth mould is a narrow rectangular channel mouth mould, and principal character is that the bevel angle of inlet is 45 degree, and narrow slit thickness is 1.0～2.0mm, and width is 5～10 with the thickness ratio.
(6) the material bar that will extrude of thermal stretch in-situ fibrillation carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～20.The traction that this thermal stretch is different from common plastics after extruding, common traction is just prepared for carrying out granulation, form to the matrix material disperse phase is uncontrollable, and the thermal stretch method can be by regulating the rotating speed of towing mechanism, obtain different hot-draw ratio (stretch ratio is defined as the ratio of the material bar sectional area behind mouthful mode cross section area and the drawn), the form of disperse phase formation fento of original position under the effect in stretching flow field, and by controlling the size (as diameter, length-to-diameter ratio etc.) that hot-draw ratio can reach control disperse phase fiber.Therefore, thermal stretch is the key factor of preparation fibrous composite with micro.
(7) force cooling extruded thing through the thermal stretch size reach stable after, immerse rapidly in the cooling trough that water temperature is lower than 25 ℃ and force cooling, the fibre shape of disperse phase is fixed up, then granulation.
The present invention processes by certain proportioning high-melting-point polyethylene terephthalate/polyester thermoplastic elastomer blend and low-melting-point polyethylene (or polypropylene) resin by the method for " melt blending is extruded-thermal stretch-quenching " provided by the invention, wherein, polyethylene terephthalate/polyester thermoplastic elastomer blend has good consistency, and the polyester thermoplastic elastomer reaches the dispersion of nanometer or submicron order yardstick in polyethylene terephthalate.The micron-sized fiber of formation of polyethylene terephthalate in the thermal stretch process/polyester thermoplastic elastomer blend original position in polyethylene (or polypropylene) matrix, and by quick cooling fento is preserved, after granulation, obtain the finished product of the present invention---polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene (or polypropylene) in-situ micro-fibril matrix material.Wherein, increase the content of polyester thermoplastic elastomer in fento, can reduce the modulus of fento and the flexibility that hardness promptly improves fento, because fento deforms on the effect meeting streamwise of shearing force field in the course of processing and is orientated, thereby this orientation and distortion can reduce fento significantly reduces melt to the mobile obstruction of polymer melt elasticity and viscosity, and the degree of fento orientation and distortion mainly is to be determined by the flexibility of fento, be orientated on the flexible bigger easier streamwise of fento, therefore the flexibility that improves fento can reduce the viscosity and the elasticity of melt, thereby can improve the processing characteristics of matrix material.
Working method provided by the invention can adopt general device of plastic processing to implement, and employed major equipment is airtight mixing machine, single screw extrusion machine or twin screw extruder, flat and mouth mould and towing mechanism that runner seamlessly transits.
The present invention has the following advantages:
(1) adopt method of the present invention to prepare polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene (or polypropylene) in-situ micro-fibril matrix material, its technology is simple, is easy to control, less demanding to equipment, employed equipment is general device of plastic processing, reduced investment.
(2) original position has formed fortifying fibre in the course of processing, makes matrix material have good comprehensive performances, higher mechanical strength, thermotolerance and other physical and mechanical propertiess.
(3) polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene (or polypropylene) in-situ micro-fibril matrix material that adopts the present invention to prepare, elasticity and modulus that can easier and quantitative control fento, thereby reduce Composite Melt elasticity and viscosity, improve the fibrous composite with micro processing characteristics, reduce the power consumption of polymer processing of material.
(4) present device is simple, and technology is easy to control, is fit to the scale production of the universal and material of this method.
Four, description of drawings
Fig. 1 is among the embodiment 4, the electron scanning micrograph of the blend brittle failure section of polyethylene terephthalate/polyester thermoplastic elastomer.
Fig. 2 is among the embodiment 6, the electron scanning micrograph of the blend brittle failure section of polyethylene terephthalate/polyester thermoplastic elastomer.
Fig. 3 removes the electron scanning micrograph of the polyethylene terephthalate/polyethylene in-situ micro-fibril matrix material of gained behind the polyethylene matrix of top layer for embodiment 3 is molten.
Fig. 4 removes the electron scanning micrograph of the polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene in-situ micro-fibril matrix material of gained behind the polyethylene matrix of top layer for embodiment 6 is molten.
Fig. 5 removes the electron scanning micrograph of the polyethylene terephthalate/polyethylene in-situ micro-fibril matrix material of gained behind the polyethylene matrix of top layer for embodiment 7 is molten.
Fig. 6 removes the electron scanning micrograph of the polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene in-situ micro-fibril matrix material of gained behind the polyethylene matrix of top layer for embodiment 10 is molten.
Fig. 7 is among Fig. 4, the electron scanning micrograph that polyethylene terephthalate/polyester thermoplastic elastomer fento surface local amplifies.
Five, embodiment
Embodiment given below is to specific descriptions of the present invention; be necessary to be pointed out that at this following examples only are used for that the present invention is described further; can not be interpreted as limiting the scope of the invention; this art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
Embodiment 1～18:
(1) dry with pet resin and polyester thermoplastic elastomer resin in 100 ℃ baking oven dry 12 hours.
(2) melting mixing earlier with polyethylene terephthalate in airtight mixing machine under 270 ℃, the rotating speed of rotor is that 10 rev/mins of fusions are after 5 minutes, add the polyester thermoplastic elastomer, after mixing 15 minutes under with 60 rev/mins rotating speed under the identical temperature, take out cooling.
(3) granulation is broken in crusher with the polyethylene terephthalate in the mixing machine/polyester thermoplastic elastomer blend.
(4) do to mix polyethylene terephthalate/polyester thermoplastic elastomer blend and polyethylene stirred at normal temperatures and mix.
(5) melting mixing, slit mouth mould are extruded and first blended material is placed the forcing machine melting mixing and are extruded, and extrusion temperature is 190～275 ℃, 275 ℃ of die temperatures, 100 rev/mins of extruder screw rotating speeds.Rectangular slot mouth mould, narrow slit thickness are 1.5mm, and width is 10 with the thickness ratio.
(6) the material bar that will extrude of thermal stretch in-situ fibrillation carries out thermal stretch under normal temperature air, regulates draw speed control hot-draw ratio.
(7) force cooling that the material bar behind the drawn is immersed in the cooling trough that water temperature is lower than 25 ℃ and force cooling, then granulation.
The prescription of table one embodiment 1～18
In order to investigate of the influence of different polyester thermoplastic elastic body burdens to melt processability, by viscosity and the elasticity (wherein in the inlet pressure at mouth mould place fall direct ratio and melt elasticity, here with inlet pressure fall the melt elasticity that characterize fibrous composite with micro) of high pressure capillary rheometer test at 170 ℃ of following sample melts.Capillary diameter 2mm, length-to-diameter ratio 16: 1, detailed numerical value see attached list two.
Table two polyethylene terephthalate/polyester thermoplastic elastomer/polyethylene (or polypropylene) in-situ micro-fibril matrix material inlet pressure at the mouth mould place under different shear rate respectively falls and viscosity
Annotate: wherein embodiment 3～6 and 7～10 can illustrate that the increase along with elastomer content in the fento can reduce the elasticity and the viscosity of melt, as comparing embodiment 6 and 3, elastomer content is 6% to be that the top hole pressure of 0.4% Composite Melt falls that (shearing rate is 33s than elastomer content
-1The time) and viscosity (shearing rate is 25s
-1The time) descended 34.1% and 24.9% respectively.
Morphologic observation: the sample that is used for morphologic observation divides two kinds, and a kind of is to adopt hot dimethylbenzene (120 ℃) dissolving 3～6 hours, and the surface that makes after washing with pure dimethylbenzene; Another kind is to use cooled with liquid nitrogen 10～20 minutes, the section that impact fracture obtains.Adopt sem observation sample form, acceleration voltage 20KV.See accompanying drawing 1～7.
Claims (4)
1. the method for preparing the controlled in-situ micro-fibril matrix material of fento flexibility is characterized in that preparing the flexible controlled in-situ micro-fibril matrix material of fento by following processing step and condition:
(1) be that 98%～70% polyethylene terephthalate and 2%～30% polyester thermoplastic elastomer prepare polyethylene terephthalate/polyester thermoplastic elastomer blend by following step (2)～(4) described processing step and condition with massfraction;
(2) dry with above-mentioned polyethylene terephthalate and polyester thermoplastic elastomer in 80～120 ℃ baking oven dry 8～24 hours, control water ratio＜0.01%;
(3) melting mixing earlier with polyethylene terephthalate in airtight mixing machine under 260～295 ℃, the rotating speed of rotor is 10～100 rev/mins, after treating complete fusion in 5～10 minutes, add the polyester thermoplastic elastomer, mixing 10～15 minutes under with 30～100 rev/mins rotating speed under the identical temperature;
(4) granulation is broken in crusher with the polyethylene terephthalate in the mixing machine/polyester thermoplastic elastomer blend, and the particle dia after the fragmentation is less than the particle of 5mm;
(5) dried mixing with polyethylene terephthalate/polyester thermoplastic elastomer blend 5%～40% and 95%～60% polyethylene or polypropylene, stirring at normal temperatures mixes, and described ratio is weight percentage;
(6) melting mixing, slit mouth mould are extruded and first blended material is placed the forcing machine melting mixing and are extruded, extrusion temperature is 150～295 ℃, 270～295 ℃ of die temperatures, 10～200 rev/mins of extruder screw rotating speeds, the big I of forcing machine is determined according to turnout, basic demand is that length-to-diameter ratio is 20～40 and does not add hybrid element, and a mouthful mould is a narrow rectangular channel mouth mould, and bevel angle 45 degree of its inlet, narrow slit thickness 1.0～2.0mm, width are 5～10 with the thickness ratio;
(7) the material bar that will extrude of thermal stretch in-situ fibrillation carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～20, and hot-draw ratio is defined as the ratio of the material bar sectional area behind mouthful mode cross section area and the drawn;
(8) force cooling extruded thing through the thermal stretch size reach stable after, immerse rapidly in the cooling trough that water temperature is lower than 25 ℃ and force cooling, the fibre shape of disperse phase is fixed up, granulation then.
2. the method for the in-situ micro-fibril matrix material that preparation fento flexibility according to claim 1 is controlled is characterized in that, in the step (2), by increasing the content of polyester thermoplastic elastomer component in the blend, reduces the Young's modulus of blend.
3. the method for the in-situ micro-fibril matrix material that preparation fento flexibility according to claim 1 is controlled, it is characterized in that, in the step (7), polyethylene terephthalate in the thermal stretch process/polyester elastomer blend forms the structure of fiber after the match at stretching action.
4. the method for the in-situ micro-fibril matrix material that preparation fento flexibility according to claim 1 is controlled, it is characterized in that, in the step (8), the material bar reaches to enter in the cold water rapidly after stable in the thermal stretch size and cools off, and the fibre shape of disperse phase can keep getting off.
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| CN102061028A (en) * | 2010-12-13 | 2011-05-18 | 四川大学 | Preparation method of conductive polymer composite with low percolation value |
| CN102492208A (en) * | 2011-12-13 | 2012-06-13 | 黑龙江省科学院技术物理研究所 | Method for modifying linear low-density polyethylene by utilizing thermoplastic polyester elastomer |
| CN107653514B (en) * | 2017-09-26 | 2020-06-09 | 江南大学 | Skin-core structure composite fiber and high-performance fiber-based composite board |
| CN108102218B (en) * | 2017-12-22 | 2020-10-02 | 南京聚隆科技股份有限公司 | High-quality automobile interior material and preparation method thereof |
| CN108559174B (en) * | 2018-03-27 | 2020-12-11 | 贵州省材料产业技术研究院 | Method for preparing high-barrier polypropylene material by regulating and controlling phase morphology and interface crystallization |
| CN108727753B (en) * | 2018-06-11 | 2021-02-05 | 中原工学院 | Preparation method of thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel |
| CN109159401B (en) * | 2018-08-27 | 2019-12-10 | 华南理工大学 | Method for blending and compatibilization of high-molecular multiphase multi-component material |
| CN113119351B (en) * | 2021-04-26 | 2023-03-21 | 肥城联谊工程塑料有限公司 | Method for preparing reclaimed material from thermoplastic composite material stretched product |
| CN115627028B (en) * | 2022-10-24 | 2023-08-08 | 郑州大学 | In-situ microfibrillated reinforced polymer composite heat insulation foam material and preparation method and application thereof |
| CN115742273B (en) * | 2022-12-07 | 2023-05-30 | 之江实验室 | Drawing preparation method of multispectral flexible self-healing optical fiber |
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| PP/弹性体共混合物与PET短纤维的复合物. 姚钟尧编译.世界橡胶工业，第31卷第4期. 2003 |
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Assignee: Chengdu Chuanke Chemical Engineering Co., Ltd. Assignor: Sichuan University Contract record no.: 2010510000063 Denomination of invention: In-site micro fibrous composite with micro fiber of controllable flexibility and its preparing method Granted publication date: 20091118 License type: Exclusive License Open date: 20070411 Record date: 20100817 |
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