CN101665603A - PP/PET in-situ microfibrillar reinforcing blend compatibilized by one-step reaction method - Google Patents
PP/PET in-situ microfibrillar reinforcing blend compatibilized by one-step reaction method Download PDFInfo
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Abstract
The description discloses a method for PP/PET in-situ microfibrillar reinforcing blend compatibilized by a one-step reaction method. The method disclosed in the invention has the following steps: PP,PET and reaction reagent are mixed according to a certain proportion, and after the processes of melt extrusion, hot drawing and quenching, the in situ compatibilized microfibrillar reinforcing blendis obtained by grain-sized dicing finally. In situ compatibilization reaction occurs in the process of melt extrusion, PET is in the form of fiber in the material. The in situ compatibilized PP/PET microfibrillar reinforcing blend has good reinforcing effect.
Description
One, technical field
The invention belongs to the novel high polymer material technical field, be to be raw material, and prepare the method that a kind of new fibrillation strengthens blend by the increase-volume of single step reaction method original position with engineering plastics polyethylene terephthalate (hereinafter to be referred as PET) and general-purpose plastics polypropylene (hereinafter to be referred as PP).
Two, background technology
In order to optimize polymer properties, people carry out blend with different polymkeric substance and prepare over-all properties than the better blend polymer of single polymers.The performance of blend polymer is influenced by each component molecular structure not only, also depends on blend phase morphology and structure to a great extent.Because most of polymkeric substance is inconsistent on thermodynamics, so in the melt-processed process, disperse phase distortion can form variform, as spherical, ellipsoid shape, bar-shaped, banded, fento shape etc.The form and the size of control disperse phase play an important role to the performance that improves blend polymer, but common method for processing forming is difficult to realize the effective control to dispersed phase morphology and size.
In the polymer blending modification process, by special method for processing forming make disperse phase in matrix on the spot (in-situ) form fortifying fibre, thereby reach the enhancing purpose, become the important channel of improving polymer performance.Because fortifying fibre forms in the course of processing on the spot, and fiber is compared small-sized (usually less than 10 μ m with macroscopic fiber, length-to-diameter ratio is greater than hundreds of), so the blend polymer that this method is obtained is defined as " fibrillation enhancing blend " (in-situ microfibrillarreinforced blend).The preparation process that fibrillation strengthens blend makes dispersed phase particles become fine on the spot exactly in the melt-processed process, its essence is to make dispersed phase particles produce moderate finite deformation and this distortion is kept.At present, prepare method that fibrillation strengthens blend mainly contain two kinds (Li Zhongming, Xu Hongsheng etc., Chinese patent, CN1944512A).Wherein, when blend is extruded, take advantage of and melt is carried out thermal stretch before uncured, make the high melting point component of disperse phase form fiber, and quenching keeps the method for getting off with fiber, be called " melt extruding-thermal stretch-quenching " method.It is continuous because have technology " to melt extrude-thermal stretch-quenching " method, is easy to control and simple relatively, and the production efficiency height obtains advantages such as practical application easily, is used to prepare thermoplastic polymer (hereinafter to be referred as TP)/TP fibrillation and strengthens blend.It is compared with TP/ macroscopic fiber (as glass, carbon fibre etc.) matrix material, have starting material wide material sources, moderate cost, processing forming good, to advantages such as equipment attrition are little, thereby be subjected to people's attention.The shortcoming that fibrillation strengthens blend is that the blend component consistency is relatively poor, and interfacial adhesion is little, and high interfacial adhesion plays crucial effects to the raising of final material mechanical performance.So how to improve the consistency that fibrillation strengthens blend, further optimize its performance, be to realize that fibrillation strengthens the key point of blend widespread use.
In blend polymer melt-processed process, add the consistency that expanding material can effectively improve blend component.Expanding material mainly is the multipolymer of grafting or block, is distributed in the phase interface place of blend in the melt-processed process substantially, can play the effect that reduces interfacial tension, increases interfacial adhesion.Yet in industrial production, design and synthesize quite difficulty of the specific incompatible blend of different expanding material increase-volumes, so adopt synthetic in advance expanding material, there is bigger limitation in the method that adds increase-volume in the blend again.And the original position increase-volume, thereby promptly in the melt-processed process, generate the method that expanding material improves the blend component consistency by reactive functional groups generation surface reaction between the polymkeric substance, owing to have advantages such as applied range, technology is simple, compatibilization effect is good, therefore obtained widespread use.At present, the original position increase-volume contains polymkeric substance and another inert polymer co-mixing system of reactive functional groups, comprises following two kinds of methods:
(1) at first will contain the monomer-grafted to inert polymer of reactive functional groups, make functionalization of polymers by the free radical grafting reaction; Then by melt-processed with functionalized polymkeric substance with contain the polymer blending of reactive functional groups, original position increase-volume reaction takes place.This method is called the increase-volume of two-step reaction method original position.
(2) blend between the functionalized and polymkeric substance of inert polymer occurs in same melt-processed process.This method is called the increase-volume of single step reaction method original position.
(Hu GH such as Hu, et al.J Appl Polym Sci, 1996,61:1039) melt extrude by twin screw, make PP graft reaction monomer glycidyl methacrylate (hereinafter to be referred as GMA) and with polybutylene terephthalate (hereinafter to be referred as PBT) blend, by the common blend of single step reaction method original position increase-volume PP/PBT, discover that the increase-volume of single step reaction method original position can effectively improve the consistency and the interfacial adhesion of PP/PBT blend, thereby the mechanical property of blend is significantly improved.(M.Pracella such as Pracella, et al.Macromol Symp, 2003,198:161) at first make GMA be grafted to PP and go up generation GMA grafted PP molecule (hereinafter to be referred as PP-g-GMA), then with PP, PET and PP-g-GMA melt blending, by the common blend of two-step reaction method original position increase-volume PP/PET.Discover that the increase-volume of two-step reaction method original position can effectively improve the consistency of blend equally, improve the mechanical property of blend.But compare with the increase-volume of single step reaction method original position, two-step reaction method original position increase-volume complex process, cost are higher.The original position increase-volume, especially single step reaction method original position increase-volume, compatibilization effect is good, and technology is continuous, is easy to control and simple relatively, the production efficiency height, cost is lower, obtains practical application easily.But the increase-volume of single step reaction method original position also is not used to the increase-volume fibrillation and strengthens blend.
Three, summary of the invention
The objective of the invention is at PP and PET incompatiblely, influence the reinforced effects that the PP/PET fibrillation strengthens blend, propose the method that single step reaction method original position increase-volume PP/PET fibrillation strengthens blend, the PP/PET fibrillation of preparation original position increase-volume strengthens blend.Melt extrude reactive functional groups generation surface reaction generation expanding material in the process, PP matrix and PET fiber interface cohesive force are improved, thereby improve the reinforced effects of PET fiber blend.
Basic raw material of the present invention is PP and PET, and PET can be commercially available any, and PP selects for use melt flow index at any of 0.3～5.0g/10min.Reaction monomers is glycidyl methacrylate (hereinafter to be referred as GMA) and vinylbenzene (hereinafter to be referred as STY), and initiator is dicumyl peroxide (hereinafter to be referred as DCP), and these reaction reagents are commercially available chemical pure.
Single step reaction method original position increase-volume PP/PET fibrillation provided by the invention strengthens the method for blend, and proportioning raw materials is in weight part, and proportioning is as follows: 100 parts of PP; 5～40 parts of PET; 0.25～1.0 part of GMA; 0.1～0.2 part of DCP; 0.2～0.8 part of STY.Single step reaction method original position increase-volume PP/PET fibrillation strengthens blend and prepares by following processing step and condition:
(1) drying is descended PET dry 8～12 hours at 100～120 ℃, makes the moisture weight content be less than 0.01%;
(2) just mixing is stirred the cooled PET of drying and PP, GMA, STY, DCP at normal temperatures by proportioning and is mixed;
(3) melting mixing is extruded and is placed the forcing machine melting mixing and extrude just mixing the material obtain, 165～275 ℃ of extruder barrel temperature, 260～270 ℃ of die temperatures, extruder screw rotating speed 60～120 commentaries on classics/min, the big I of forcing machine is determined according to turnout, basic demand is, length-to-diameter ratio is 20～40, the bevel angle of mouth mould inlet is 45 degree, and to the circular port mould, length-to-diameter ratio is 5～10, diameter is 1.0～2.0cm, to narrow rectangular channel mouth mould, narrow slit thickness is 1.0～2.0mm, and width is 5～10 with the thickness ratio;
(4) the material bar that will extrude of thermal stretch carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～10, and the towing mechanism adjustable speed to be obtaining different hot-draw ratios, and hot-draw ratio is defined as the ratio of mouthful mode cross section area and material bar sectional area after thermal stretch;
(5) force cooling will the material bar after thermal stretch to be immersed in the water coolant that temperature is lower than 20 ℃ and force cooling;
(6) the cooled material bar of pelletizing is through the dicing machine pelletizing.
The present invention processes high melt point thermoplastic polymer P ET and low melting point thermoplastic polymer PP according to a certain ratio by " melt extruding-thermal stretch-quenching " method, and realizes the increase-volume of single step reaction method original position.Original position increase-volume reaction takes place in melt extruding process: at first under the initiator DCP effect, the reaction monomers GMA that contains two keys and epoxide group passes through the free radical grafting reactive grafting to the PP molecular chain, generates PP-g-GMA; At the interface, the end carboxyl generation chemical reaction of epoxide group on the PP-g-GMA and PET generates PP grafting PET multipolymer (hereinafter to be referred as PP-g-PET) then, and PP-g-PET can play the effect of expanding material.Meanwhile, disperse phase PET melt extrude with the shearing of thermal stretch and drawing force field action under form the fiber of micron or submicron order on the spot, thereby PP-g-PET realizes the original position increase-volume to PET fiber and PP matrix.At last, extrudate is preserved fiber get off by quick cooling, obtains the finished product of the present invention after pelletizing---and the PP/PET fibrillation of single step reaction method original position increase-volume strengthens blend.Single step reaction method original position increase-volume PP/PET fibrillation strengthens blend, the compatible lover of PET fiber with the PP matrix, the interfacial adhesion height, this blend can extrude, in the reprocessing process such as injection moulding, mold pressing, the fibrous texture that keeps its original position increase-volume, thus played more efficiently enhancement for material.
Four, advantage of the present invention
Working method provided by the invention can adopt general polymer processing equipment to implement, and employed major equipment is 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 single step reaction method original position increase-volume PP/PET fibrillation and strengthen blend, compatibilization effect is remarkable, and interfacial adhesion is significantly improved, and the PP/PET fibrillation strengthens the performance of blend and further optimized.
(2) adopt method of the present invention to prepare single step reaction method original position increase-volume PP/PET fibrillation and strengthen blend, its technology is simple, is easy to control, less demanding to equipment, and employed equipment is general polymer processing equipment, reduced investment.
(3) adopt method preparation preparation single step reaction method original position increase-volume PP/PET fibrillation of the present invention to strengthen blend, shortened technical process, save the energy, improved production efficiency, be easy to apply.
(4) adopt method of the present invention to prepare single step reaction method original position increase-volume PP/PET fibrillation and strengthen blend the tensile strength and the tensile modulus of PP/PET blend had good enhancement, industrial application value is bigger.
Five, description of drawings
Fig. 1 is the common blend injection moulding of the PP/PET of comparative example 2 a batten brittle failure profile scanning electron micrograph.
Fig. 2 is that the PP/PET fibrillation of comparative example 3 strengthens blend injection moulding batten brittle failure profile scanning electron micrograph.
Fig. 3 is the common blend injection moulding of the single step reaction method original position increase-volume PP/PET batten blend injection moulding batten brittle failure profile scanning electron micrograph of comparative example 1.
Fig. 4 is that the single step reaction method original position increase-volume PP/PET fibrillation of embodiment 4 strengthens blend injection moulding batten brittle failure profile scanning electron micrograph.
Fig. 5 goes the PP/PET fibrillation of gained behind the PP matrix of top layer to strengthen the electron scanning micrograph of blend for comparative example 3 is molten.
Fig. 6 goes the single step reaction method original position increase-volume PP/PET fibrillation of gained behind the PP matrix of top layer to strengthen the electron scanning micrograph of blend for embodiment 4 is molten.
Six, the specific embodiment of the invention
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 further illustrated; can not be interpreted as limiting the scope of the invention, this art skilled person still belongs to protection scope of the present invention according to the invention described above content to nonessential improvement and the adjustment that the present invention makes.
Embodiment 1～16:
(1) drying is descended PET dry 12 hours at 120 ℃, makes the moisture weight content be less than 0.01%.
(2) just mixing is stirred the cooled PET of drying and PP, GMA, STY, DCP at normal temperatures by proportioning and is mixed.Prescription sees attached list one.
(3) melting mixing is extruded and will just be mixed the material obtain to place screw slenderness ratio be 25: 1 single screw extrusion machine melting mixing and extrude, and the temperature of first three section of barrel and mouthful mould is set at 165,265,275,270 ℃ respectively.The mouth mould is selected flat narrow slot mould for use, and narrow slit thickness is 1.5mm, and width is 10 with the thickness ratio.The extruder screw rotating speed is 65 commentaries on classics/min.
(4) the material bar that will extrude of thermal stretch carries out thermal stretch under normal temperature air, and hot-draw ratio sees attached list one.
(5) force cooling that pressure cooling in the water coolant that is lower than 20 ℃ is stablized in the material bar immersion after thermal stretch.
(6) the cooled material bar of pelletizing is through the dicing machine pelletizing.
Comparative example 1～3:
(1) comparative example 1～2, the set of dispense ratio that provides by comparative example in the table 1 1～2, with material according to processing step and the machined parameters of embodiment 1～16 carry out just mixing, melting mixing extrudes, forces cooling and pelletizing, but do not carry out thermal stretch, both hot-draw ratio was 1.
(2) comparative example 3, and the set of dispense that provides by comparative example in the table 13 is hot-draw ratio when, with material according to processing step and the machined parameters of embodiment 1～16 just mix, melting mixing is extruded, thermal stretch, pressure cooling and pelletizing.
The prescription of table one embodiment 1～16 and comparative example 1～3
Annotate: PP, PET, GMA, DCP and STY are weight part.
Strengthen the physical and mechanical properties of blend for the single step reaction method original position increase-volume PP/PET fibrillation of investigating the present invention's preparation, the blend of gained is placed injection moulding machine, Shooting Technique condition routinely is injection molded into the standard tensile batten, and carries out the tensile property test.
The tensile property test: adopt the ASTM-638 standard, rate of extension is 50mm/min, and temperature is 25 ± 2 ℃.See attached list two.
The blend tensile property of table two embodiment 1～19 and comparative example 1～3
| Material category | Tensile strength (MPa) | Tensile modulus (GPa) |
| Embodiment 1 | ??35.7 | ??1.02 |
| Embodiment 2 | ??33.4 | ??1.37 |
| Embodiment 3 | ??36.3 | ??2.22 |
| Embodiment 4 | ??37.5 | ??2.76 |
| Embodiment 5 | ??35.9 | ??2.54 |
| Embodiment 6 | ??34.8 | ??2.32 |
| Embodiment 7 | ??37.9 | ??2.80 |
| Embodiment 8 | ??38.3 | ??2.83 |
| Embodiment 9 | ??33.1 | ??2.51 |
| Embodiment 10 | ??33.0 | ??2.17 |
| Embodiment 11 | ??35.3 | ??2.45 |
| Embodiment 12 | ??37.2 | ??3.03 |
| Embodiment 13 | ??36.9 | ??2.67 |
| Embodiment 14 | ??38.2 | ??2.85 |
| Embodiment 15 | ??36.7 | ??2.60 |
| Embodiment 16 | ??35.6 | ??2.44 |
| Comparative example 1 | ??36.6 | ??2.50 |
| Comparative example 2 | ??28.5 | ??1.66 |
| Comparative example 3 | ??32.0 | ??2.12 |
Morphologic observation: the sample that is used for morphologic observation is divided into two kinds, and a kind of is dimethylbenzene (125～130 ℃) dissolving 10～15 hours of adopting heat, and the surface that makes after washing with pure dimethylbenzene; Another kind is that blend injection moulding batten is placed the brittle failure section that brittle failure makes behind the liquid nitrogen deep cooling 15min.Adopt sem observation sample form, acceleration voltage 20KV.See accompanying drawing 1～6.Accompanying drawing 1 is the common blend injection moulding of the PP/PET batten brittle failure section of comparative example 2, the spherical in shape or elliposoidal distribution of disperse phase PET particle, and phase interface is obvious; Accompanying drawing 2 is that the PP/PET fibrillation of comparative example 3 strengthens blend injection moulding batten brittle failure section, and disperse phase PET is fibrous distribution, and a large amount of fibrous terminations appears in section, and interfacial adhesion is relatively poor.Accompanying drawing 3 is the common blend injection moulding of the single step reaction method original position increase-volume PP/PET batten brittle failure section of comparative example 1, and disperse phase PET particle diameter reduces, distributes and becomes evenly, and the interface is fuzzy, proves that the original position compatibilization effect is obvious.Accompanying drawing 4 is that the single step reaction method original position increase-volume PP/PET fibrillation of embodiment 4 strengthens blend injection moulding batten brittle failure section, has a large amount of fibrous terminations, illustrates that disperse phase PET still can form fiber under the original position increase-volume condition; Fig. 5 goes to the surface that the PP/PET fibrillation of gained strengthens blend behind the PP matrix of top layer for comparative example 3 is molten, PET fiber length-to-diameter ratio is bigger; Fig. 6 goes to the surface that the single step reaction method original position increase-volume PP/PET fibrillation of gained strengthens blend behind the PP matrix of top layer for embodiment 4 is molten, PET fiber length-to-diameter ratio diminishes under the original position increase-volume condition, but from mechanics property analysis, this PET fiber still plays crucial effects to tensile strength and the tensile modulus that improves blend.
Claims (4)
1. single step reaction method original position compatibilized polypropylene provided by the invention (hereinafter to be referred as PP)/polyethylene terephthalate (hereinafter to be referred as PET) fibrillation strengthens the method for blend, it is characterized in that the PP/PET fibrillation for preparing the increase-volume of single step reaction method original position by following processing step and condition strengthens blend:
(1) weighing takes by weighing feed composition by following formulation by weight:
PP:100 part; PET:5～40 part; Glycidyl methacrylate (hereinafter to be referred as GMA): 0.25～1.0 part; Vinylbenzene (hereinafter to be referred as STY): 0.2～0.8 part; Dicumyl peroxide (hereinafter to be referred as DCP): 0.1～0.2 part;
(2) drying is descended PET dry 8～12 hours at 100～120 ℃, makes the moisture weight content be less than 0.01%;
(3) mixing is just stirred the cooled PET of drying and PP, the GMA, STY, the DCP that take by weighing by above-mentioned prescription at normal temperatures and is mixed;
(4) melting mixing is extruded and is placed the forcing machine melting mixing and extrude just mixing the material obtain, 165～275 ℃ of extruder barrel temperature, 260～270 ℃ of die temperatures, extruder screw rotating speed 60～120 commentaries on classics/min, the big I of forcing machine is determined according to turnout, basic demand is, length-to-diameter ratio is 20～40, the bevel angle of mouth mould inlet is 45 degree, and to the circular port mould, length-to-diameter ratio is 5～10, diameter is 1.0～2.0cm, to narrow rectangular channel mouth mould, narrow slit thickness is 1.0～2.0mm, and width is 5～10 with the thickness ratio;
(5) the material bar that will extrude of thermal stretch carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～10, and the towing mechanism adjustable speed to be obtaining different hot-draw ratios, and hot-draw ratio is defined as the ratio of mouthful mode cross section area and material bar sectional area after thermal stretch;
(6) force cooling will the material bar after thermal stretch to be immersed in the water coolant that temperature is lower than 20 ℃ and force cooling;
(7) the cooled material bar of pelletizing is through the dicing machine pelletizing.
2. single step reaction method original position increase-volume PP/PET fibrillation according to claim 1 strengthens the method for blend, it is characterized in that melting mixing, extrude with the thermal stretch process in, PET has formed microfibrillar structure in PP.
3. single step reaction method original position increase-volume PP/PET fibrillation according to claim 1 strengthens the method for blend, it is characterized in that the reaction monomers GMA and the STY that add are melt extruding in the process when melting mixing is extruded, under the initiator DCP effect, chemical reaction has taken place with PP and PET, the original position increase-volume PP/PET fibrillation strengthen blend.
4. single step reaction method original position increase-volume PP/PET fibrillation according to claim 1 strengthens the method for blend, and the PP/PET fibrillation that it is characterized in that the increase-volume of single step reaction method original position strengthens blend has good enhancement to the tensile strength and the tensile modulus of PP/PET blend.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167866A (en) * | 2011-03-08 | 2011-08-31 | 四川大学 | Method for inhibiting skin core structure of polypropylene injection molding product |
| CN102875737A (en) * | 2012-10-19 | 2013-01-16 | 上海纽克新材料科技有限公司 | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof |
| CN107118309A (en) * | 2017-06-26 | 2017-09-01 | 浙江海轩科技有限公司 | A kind of biodegradable polyesters alloy and preparation method thereof |
| US11584820B2 (en) | 2020-03-13 | 2023-02-21 | Industrial Technology Research Institute | Polymer blend and fiber |
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2009
- 2009-09-28 CN CN200910167780A patent/CN101665603A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167866A (en) * | 2011-03-08 | 2011-08-31 | 四川大学 | Method for inhibiting skin core structure of polypropylene injection molding product |
| CN102875737A (en) * | 2012-10-19 | 2013-01-16 | 上海纽克新材料科技有限公司 | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof |
| CN102875737B (en) * | 2012-10-19 | 2014-12-03 | 上海纽克新材料科技有限公司 | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof |
| CN107118309A (en) * | 2017-06-26 | 2017-09-01 | 浙江海轩科技有限公司 | A kind of biodegradable polyesters alloy and preparation method thereof |
| US11584820B2 (en) | 2020-03-13 | 2023-02-21 | Industrial Technology Research Institute | Polymer blend and fiber |
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