CN107254149B - Soft nanometer microcell toughened PET composite material and preparation method thereof - Google Patents
Soft nanometer microcell toughened PET composite material and preparation method thereof Download PDFInfo
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- CN107254149B CN107254149B CN201710545681.3A CN201710545681A CN107254149B CN 107254149 B CN107254149 B CN 107254149B CN 201710545681 A CN201710545681 A CN 201710545681A CN 107254149 B CN107254149 B CN 107254149B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/006—Additives being defined by their surface area
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Abstract
The invention discloses a kind of soft nanometer microcell toughened PET composite materials and preparation method thereof, the toughened PET composite material includes following mass percent component: polyethylene terephthalate 80~93%, porosity nano inorganic powder 1~5%, liquid-state oligomers 5~10%, polarity graft 1~5%, appropriate antioxidant.PET is worn into powdery by the present invention after cooling, nano inorganic powder is impregnated using liquid-state oligomers, nano inorganic powder is impregnated sufficiently by liquid-state oligomers to absorb, form the soft ball-type nanostructure but also with elasticity, and select the wetting characteristics on polarity graft improvement nano inorganic powder surface, it can be dispersed in PET matrix, soft nanometer microcell plays the effect of toughening in PET.The PET sheet for adding toughening composition production of the invention has excellent impact property, and maintains good optical property.
Description
[technical field]
The present invention relates to soft nanometer microcell toughened PET composite materials and preparation method thereof, belong to PET modified material technology
Field.
[background technique]
Polyethylene terephthalate (english abbreviation: PET) has excellent electrical insulating property, heat resistance and chemically-resistant medicine
The excellent properties such as moral character are widely used to the production fields such as fiber, film and sheet material.PET material price is low, comprehensive performance
It is excellent, it is easily recycled, has the stronger market competitiveness than polyvinyl chloride (PVC) not environmentally, therefore, there is PET material in market
Gradually substitute the trend of PVC.But since PET enbrittles the disadvantages of big, impact property is poor, it is limited in packaging, electronics, electricity
The application in the fields such as device, automobile, machinery.
The polyethylene terephthalate composite material and its system of Chinese patent ZL200810198221.9 toughening modifying
Preparation Method discloses a kind of high tenacity polyethylene terephthalate composite material and preparation method.Its main component include with
Under: PET matrix, elastomer, inorganic nano material and surface treating agent, and elastomer packet is obtained using fairly simple method
Soft shell-monocoque of filler is covered, so that the composite material with high tenacity and high stiffness be made.Realize elastomer, nanometer
Calcium carbonate coordination plasticizing polyethylene terephthalate, expands its application range, and reduces the cost of material.But pass through
Although the inorganic nano material of surface treatment reduces intermolecular reunion, but poor with PET interface interaction, loses nanoparticle
Ideal toughening effect is not achieved in the characteristics of high activity.
Chinese patent ZL200410017174.5 also discloses a kind of high tenacity polyethylene terephthalate blend
And preparation method thereof.The group of this high tenacity PET blend becomes PET, the elastomer containing epoxy group and nitrogenous crosslinking
Agent.Mentioned component is added in double screw extruder under 250-300 DEG C of processing temperature, while shear-mixed, is handed over
Ring-opening reaction can be occurred with epoxy group by joining agent, make to have the elastomer crosslinked of epoxy group, the elastomer of crosslinking is dispersed in PET
In continuous phase, the shock resistance of PET can be improved, but also result in system rigidity, intensity, heat resistance simultaneously etc. it is serious under
Drop.
To sum up, it is being mentioned whether by elastic body toughening still with the method for inorganic nano material collaboration elastic body toughening
Influence when not accounting for composite toughening while high toughening effect to the product transparency.
[summary of the invention]
The purpose of the present invention is to overcome the shortcomings of the prior art and to provide one kind can be added into the soft of PET sheet production
Nanometer microcell toughened PET composite material can make PET sheet realize the effect of toughening, and keep good optical property.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned toughened PET composite material.
The purpose of the present invention is what is be achieved through the following technical solutions:
Soft nanometer microcell toughened PET composite material, it is characterised in that including following mass percent component:
The intrinsic viscosity of polyethylene terephthalate in the present invention is 0.65~0.80dl/g, preferred characteristics viscosity number
For 0.76dl/g.
Porosity nano inorganic powder in the present invention is nanometer calcium carbonate or nano silica, the porosity nanometer
The partial size of inorganic particle is 15~50nm, and preferable particle size is 30~50nm, and the specific surface area of porous nano inorganic particle exists
150m2/ g or more.There is nano inorganic powder powerful specific surface energy to cause interparticle reunion, and partial size is smaller, and reunion is got over
Seriously, it is less susceptible to be uniformly dispersed.
Liquid-state oligomers in the present invention are polyurethane resin oligomer, acrylic resin oligomer, vinyl acetate resin
One of oligomer；Oligomer in the present invention refers to the polymer as composed by 10-20 repetitive unit.
Soft nanometer microcell toughened PET composite material in the present invention, it is characterised in that the polarity graft is
One of POE-g-MAH, EPDM-g-MAH, SEBS-g-MAH.
Nano inorganic powder, particle surface is hydrophilic and oleophobic, poor with continuous phase PET interface binding power, when by external force
When impact, boundary defect is easily caused, material property is caused to decline, therefore, is made using liquid-state oligomers dipping nano inorganic powder
It can be sufficient filling with, and obtain the nano inorganic powder full of liquid-state oligomers, have the effect of elastomer.But simple dipping
Nano inorganic powder and the weaker problem of continuous phase PET interface binding power afterwards is also unresolved.Therefore, it is also desirable to nano inorganic
Powder carries out graft modification, carries out surface using polarity graft and is modified, effectively prevents the reunion of nano inorganic powder, improve it
Dispersibility.This kind of polarity grafts such as selection POE-g-MAH, EPDM-g-MAH, SEBS-g-MAH can improve nano inorganic powder
The wetting characteristics of body can make it have charge characteristic and form adsorption layer with oriented attachment on nano inorganic powder surface, prevent
Agglomeration occurs for nano inorganic powder, so as to improve dispersibility of the nano inorganic powder in continuous phase.
Such as: the CO on nanometer calcium carbonate surface3 2-Ion has biggish ratio that can be replaced by the water adsorption in atmosphere, and
Hydrolysis.Reaction process is as follows:
Nano-calcium carbonate particles after surface grafting act on PET composite material, can be adsorbed on pet sheet face, receive
Rice calcium carbonate is doped between polyester molecule, is kept strand arrangement loose, is increased the contact area with matrix, so as to improve its dispersion
Property.And its skin effect can also make calcium carbonate and polyester molecule form stronger chemical bond or hydrogen bond, change polyester molecule table
Planar orientation, the interface binding intensity of enhancing and polyester polymers.
Porosity nano-calcium carbonate particles after surface graft modification can be very good the micropore and ditch in filling pet sheet face
Slot improves polymer surfaces density, reduces material and generates void defects in recombination process.Additionally, due to nanometer calcium carbonate
It is preferable in surface of polyester degree of scatter, and it contains hydroxyl, and hydrogen can be partially formed in the interfacial structure constituted with graft
Key and covalent bond reduce stress concentration phenomenon when matrix stress, have effectively played nano particle reinforced tenacity increased effect.
Equally there is great amount of hydroxy group on the surface of nano silica, has good affinity interaction with polarity graft.
The preparation method of the above-mentioned soft nanometer microcell toughened PET composite material of the present invention, it is characterised in that including following
Step:
A, after polyethylene terephthalate is cooling under Cryogenic Conditions, shape of claying into power is spare；
B, porosity nano inorganic powder is impregnated with liquid-state oligomers, time of infusion again after stirring, 2 hours left sides
The right side makes liquid-state oligomers sufficiently infiltrate filling nano inorganic powder, forms soft ball-type nano material；
C, polyethylene terephthalate powder, soft ball-type nano material are uniformly mixed with polarity graft, are passed through
By the melting extrusion of dual-screw-stem machine extruder, dry cooling, granulation.
Toughened PET composite material prepared by the present invention has the structure on similar island, as shown in Figure 1.
In preparation method step a of the present invention, the cooling Cryogenic Conditions of polyethylene terephthalate are the cooling 3-5 of liquid nitrogen
Minute, minimum temperature can be down to minus 196 DEG C.
Polyethylene terephthalate is clayed into power under Cryogenic Conditions in the present invention, is formed well with other materials
First dispersion, prevent nano-inorganic substance from reuniting as far as possible.
The soft ball-type nanostructure that the present invention is formed after impregnating porosity nano inorganic powder with liquid-state oligomers, makes
Originally the biggish nano inorganic powder particle of rigidity forms a soft ball shape structure, elasticity after being filled by liquid-state oligomers
Body graft coats ball-type inorganic nano material, can bear more impact energys, have the function that toughening.Polarity graft is excellent
It is selected as powdery mixing, if the raw material that purchase is practised is graininess, powdery is first worn into and reuses.
In preparation method of the present invention, for temperature range control when double screw extruder produces at 180~275 DEG C, host is electric
For flow control in 30~40A, engine speed and feeding control are 300~350r/min and 20~30HZ, melt pressure control respectively
In 0.5~1.0MPa.
Specifically, specifically each area's temperature range control is as follows for double screw extruder: I 180~190 DEG C of area's temperature, II area 210
~230 DEG C, 230~250 DEG C of III area's temperature, 260~270 DEG C of IV area's temperature, 260~270 DEG C of V area's temperature, VI area's temperature 260
~270 DEG C, 255~265 DEG C of VII area's temperature, 255~265 DEG C of VIII area's temperature, 255~265 DEG C of Ⅸ area's temperature, die head temperature be
265~275 DEG C.
The present invention compared with the existing technology, has the advantages that
PET is worn into powdery by the present invention after cooling, the nano inorganic powder impregnated with liquid-state oligomers and elastomer pole
Property graft act synergistically on PET, so that it is being reached excellent toughening effect, using liquid-state oligomers impregnate nano inorganic powder,
It impregnates nano inorganic powder sufficiently by liquid-state oligomers to absorb, forms the soft ball-type nanostructure but also with elasticity, and select
Improve the wetting characteristics on nano inorganic powder surface with polarity graft, this kind of polarity graft can directionally be adsorbed on nanometer
Inorganic powder surface makes it have charge characteristic and forms adsorption layer, declines nano inorganic powder agglomeration tendency, reach
The effect for improving nano inorganic powder dispersibility, enables nano inorganic powder to be dispersed in PET matrix, soft nanometer
Microcell plays the effect of toughening in PET.
The PET sheet for adding toughening composition production of the invention has excellent impact property, and maintains good
Optical property.
[Detailed description of the invention]
Fig. 1 is the structure chart of toughened PET composite material of the present invention；
1 is a nanometer microcell, and 2 be PET matrix；Nanometer microcell is after nano particle impregnates oligomer, with nano-grade size point
It is dispersed in formation toughening microcell phase in PET matrix；PET matrix is the continuous phase that polyethylene terephthalate is formed.
[specific embodiment]
Invention is further described in detail combined with specific embodiments below:
Embodiment 1:
Embodiment 2:
Embodiment 3:
Embodiment 4:
Embodiment 5:
Embodiment 1-5's the preparation method comprises the following steps:
After first that polyethylene terephthalate is cooling under Cryogenic Conditions, shape of claying into power, specific implementation method is:
First graininess PET is smashed, then wears into powdery with plastic grinder.
Porosity nano inorganic powder is impregnated with liquid-state oligomers simultaneously, stirs time of infusion.Make liquid oligomeric
Object can be sufficient filling with nano inorganic powder, form soft ball-type nanostructure, make the biggish nano inorganic powder of rigidity originally
Particle forms a soft ball shape structure, can bear more impact energys, reach toughening after being filled by liquid-state oligomers
Effect.
Finally, each component raw material is mixed in proportion to form blend, via double screw extruder melting extrusion, dry
Dry cooling, granulating and forming.
Wherein the host current control of double screw extruder controls respectively in 40A, engine speed and the control of feeding revolving speed
300r/min and 30HZ, in 1.25MPa, pelleter revolving speed is 328r/min for melt pressure control, and each area's temperature control is such as 1 institute of table
Show:
Table 1:
| 1 area DEG C | 2 areas DEG C | 3 areas DEG C | 4 areas DEG C | 5 areas DEG C |
| 185 | 230 | 250 | 268 | 268 |
| 6 areas DEG C | 7 areas DEG C | 8 areas DEG C | 9 areas DEG C | Die head temperature DEG C |
| 268 | 268 | 265 | 265 | 273 |
The technological parameter of double screw extruder of the present invention belongs to conventional parameter ranges, and embodiment is just not listed one by one.
Embodiment 1-5 prepares soft nanometer microcell toughened PET composite material, adds respectively in pure PET as toughener
1% toughening material of the present invention is added to prepare PET sheet, the PET sheet of Application Example 1-5 adds the increasing of embodiment 1-5 respectively
Tough material, Application Example 1-5 and the PET sheet for using pure PET to prepare for not adding material of the present invention are carried out as blank sample
Performance control test.Test result is as shown in table 2.
Table 2: embodiment is compareed with blank sample result
Result can be seen that using soft nanometer microcell toughened PET composite material prepared by the present invention in not shadow from table 2
Under conditions of clicker material optical property itself, sheet material impact strength highest can be made to improve 9.48%, low temperature impact strength highest
It can be improved 42.44%.
Toughened PET composite material of the present invention improves PET sheet as a kind of addition of toughener for producing PET sheet
Room temperature and low-temperature impact resistance, while keeping the optical property of PET sheet.
Claims (6)
1. soft nanometer of microcell toughened PET composite material, it is characterised in that including following mass percent component:
The intrinsic viscosity of the polyethylene terephthalate is 0.65~0.80dl/g, the porosity nano inorganic
Powder is nanometer calcium carbonate or nano silica, and the partial size of the porosity nano inorganic powder is 15~50nm；
Preparation method includes the following steps:
A, after polyethylene terephthalate is cooling under Cryogenic Conditions, shape of claying into power is spare；
B, porosity nano inorganic powder is impregnated with liquid-state oligomers, time of infusion again after stirring makes liquid-state oligomers
Sufficiently infiltration filling nano inorganic powder, forms soft ball-type nano material；
C, polyethylene terephthalate powder, soft ball-type nano material are uniformly mixed to be formed and are blended with polarity graft
Object, via the melting extrusion of dual-screw-stem machine extruder, dry cooling, granulation.
2. soft nanometer microcell toughened PET composite material according to claim 1, it is characterised in that the liquid oligomeric
Object is one of polyurethane resin oligomer, acrylic resin oligomer, vinyl acetate resin oligomer.
3. soft nanometer microcell toughened PET composite material according to claim 1, it is characterised in that the polarity grafting
Object is one of POE-g-MAH, EPDM-g-MAH, SEBS-g-MAH.
4. soft nanometer microcell toughened PET composite material according to claim 1, it is characterised in that the Cryogenic Conditions are
Liquid nitrogen is cooling, and the partial size of powdered polyethylene terephthalate is 1~5 μm.
5. soft nanometer microcell toughened PET composite material according to claim 1, it is characterised in that the twin-screw extrusion
Temperature range control when machine produces is at 180~275 DEG C, and host current control is in 30~40A, engine speed and feeding control point
It is not 300~350r/min and 20~30Hz, melt pressure is controlled in 0.5~1.0MPa.
6. soft nanometer microcell toughened PET composite material according to claim 1, it is characterised in that the twin-screw extrusion
Specifically each area's temperature range control is as follows for machine: I 180~190 DEG C of area's temperature, 210~230 DEG C of IIth area, III area's temperature 230~250
DEG C, 260~270 DEG C of IV area's temperature, 260~270 DEG C of V area's temperature, 260~270 DEG C of VI area's temperature, VII area's temperature 255~265
DEG C, 255~265 DEG C of VIII area's temperature, 255~265 DEG C of Ⅸ area's temperature, die head temperature be 265~275 DEG C.
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Effective date of registration: 20230103 Address after: Room 230, No. 39-2, Keji East Road, Torch Development Zone, Zhongshan, Guangdong 528400 Patentee after: Zhongshan Jinggong Polymer Materials Co.,Ltd. Address before: 528400 Block A, No.1 Gangyi Road, Torch Development Zone, Zhongshan City, Guangdong Province Patentee before: ZHONGSHAN BEIHUA POLYMER MATERIALS CO.,LTD. |