CN107522941A - A kind of heat resistant transparent anti-impact PVDF/PP alloy materials and preparation method thereof - Google Patents
A kind of heat resistant transparent anti-impact PVDF/PP alloy materials and preparation method thereof Download PDFInfo
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- CN107522941A CN107522941A CN201710627573.0A CN201710627573A CN107522941A CN 107522941 A CN107522941 A CN 107522941A CN 201710627573 A CN201710627573 A CN 201710627573A CN 107522941 A CN107522941 A CN 107522941A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of heat resistant transparent anti-impact PVDF/PP alloy materials and preparation method thereof.The PVDF/PP alloy materials are by acrylic resin, polyvinylidene fluoride resin, lubricant, antioxidant and nucleator composition.Also disclose that a kind of preparation method of heat resistant transparent anti-impact PVDF/PP alloy materials simultaneously.The present invention is by the way of PVDF and PP materials make alloy, the combination property of acquisition is than single PP resins, and the performance than adding transparent nucleater MODIFIED PP is more excellent, and especially heat-resisting and impact property improves obvious, it can be applied to the product such as heat-resisting industrial container, washing machine transparency window.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of heat resistant transparent anti-impact PVDF/PP alloy materials and its
Preparation method.
Background technology
Polypropylene (PP) has the stable row of good chemically-resistant and processability, cheap, so using than wide.But
In some aspects, its application is by transparent and temperature capability is inadequate is limited.
Existing mode is by adding nucleator, accelerating PP crystalline rate so that fine grain size, so as to obtain
Obtain the high transparency of PP materials.Recent domestic is used for improving the transparent nucleater of the PP transparencys, can not only improve product
Rigidity, but also the transparency and glossiness of product can be increased.
In Europe, transparent PP is used to substitute polyvinyl chloride (PVC) and polystyrene (PS) packaging material, and it, which has, mitigates weight
Measure and reduce the potentiality of cost.In Japan, transparent PP is answered in terms of industrial container, injector for medical purpose, video-tape and floppy disk
With.Compared with PS industrial container products, transparent PP occurs that the problem of breakage is less in use, and its humidity resistance
It it is 10 times of PS or so and density is 85% of PS or so.Goblet, CD packing boxes, vitamin bottle packing articles side
Face, transparent PP material is than other materials advantageously.
Nucleator is added in PP, in crystallization process original homogeneous nucleation can be made to become heterogeneous nucleation, be formed in PP
In multiple nucleus points, make nucleation while occur, reduce crystallization time, refine spherocrystal.Spherocrystal is formed in PP cooling procedures,
And certain interface is readily formed between these spherocrystals, due to refractive index of the visible ray between spherocrystal crystalline portion and interface not
It is identical, optical haze easily is internally formed in spherocrystal, influences the PP transparency.Spherocrystal is trickleer, and its particle diameter is with regard to smaller, the interface between spherocrystal
Also it is just smaller, it is seen that light hardly reflects on crystalline region interface, if the particle diameter of crystal grain is less than the wavelength of visible ray, now may be used
See that light does not also reflect.Nucleator, which is added in PP, is used as out-phase nucleus, accelerates PP crystallization rate, and refinement finishes Jingjing
Grain, so as to reduce the refraction of visible ray and reflection, improves PP transparency and glossiness.
Add transparent nucleater so that the transparency of PP materials increases, but still suffers from the problem of impact is relatively low.Although
By adding toughener, raising COPP or beta nucleater etc. can improve the impact property of polypropylene material, but material
Transparency, rigidity and heat resistance can reduce.It is restricted needing heat-resisting industrial container and micro-wave oven transparency window etc..
In summary, find a kind of polypropylene material preparation method for material of heat resistant transparent anti-impact and seem extremely important.
The content of the invention
It is an object of the invention to provide a kind of heat resistant transparent anti-impact PVDF/PP alloy materials and preparation method thereof.
The technical solution used in the present invention is：
A kind of heat resistant transparent anti-impact PVDF/PP alloy materials, are made up of the raw material of following mass percent：88.5~
98.3% acrylic resin, 1.0~10.0% polyvinylidene fluoride resins, 0.2~0.5% lubricant, 0.4~0.6% antioxidant,
0.1~0.4% nucleator.
The MFR of acrylic resin is (3~50) g/10min.
The MFR of polyvinylidene fluoride resin is (0.5~5) g/10min.
Lubricant be stearic acid, stearate, fatty acid amide, stearate, ethylene-vinyl acetate copolymer, ethene-
At least one of acrylic copolymer.
Antioxidant is antioxidant 1010 and irgasfos 168 in mass ratio 1：(1~2) compound antioxidant of composition.
Nucleator is at least one of Sorbitol Nucleator, nucleator in organic phosphate class.
A kind of preparation method of heat resistant transparent anti-impact PVDF/PP alloy materials, raw material is weighed by above-mentioned composition, mixing,
Extrusion, it is granulated, obtains heat resistant transparent anti-impact PVDF/PP alloy materials.
Twin-screw extrusion is extruded as, the parameter of double screw extruder is：One area's temperature is 180~200 DEG C；Two area's temperature are
185~205 DEG C；Three area's temperature are 190~210 DEG C；Four area's temperature are 185~205 DEG C；Five area's temperature are 185~205 DEG C；Six
Area's temperature is 185~205 DEG C；Seven area's temperature are 180~200 DEG C；Eight area's temperature are 180~200 DEG C；Head temperature 200~220
℃；Material residence time in double screw extruder is 0.5~1.5min；Vacuum -0.04~-0.06Mpa.
The beneficial effects of the invention are as follows：
1st, by the way of PVDF and PP materials make alloy, the combination property of acquisition is more saturating than adding than single PP resins
Bright nucleater modified PP performance is more excellent, and especially heat-resisting and impact property improves substantially, can be applied to heat-resisting industry and holds
The product such as device, washing machine transparency window；
2nd, simple production process of the invention, it is easy to operate.
Embodiment
A kind of heat resistant transparent anti-impact PVDF/PP alloy materials, are made up of the raw material of following mass percent：88.5~
98.3% acrylic resin, 1.0~10.0% polyvinylidene fluoride resins, 0.2~0.5% lubricant, 0.4~0.6% antioxidant,
0.1~0.4% nucleator.
Preferably, a kind of heat resistant transparent anti-impact PVDF/PP alloy materials, are made up of the raw material of following mass percent：
96~98% acrylic resins, 2.0~4.0% polyvinylidene fluoride resins, 0.2~0.4% lubricant, 0.4~0.5% antioxygen
Agent, 0.2~0.3% nucleator.
Preferably, acrylic resin is HOPP resin, and the MFR (melt mass flow rate) of acrylic resin is
(3~50) g/10min.
Preferably, the MFR of polyvinylidene fluoride resin is (0.5~5) g/10min.
Preferably, lubricant is stearic acid, stearate, fatty acid amide, stearate, ethene-vinyl acetate copolymerization
At least one of thing, ethylene-acrylic acid copolymer；It is further preferred that lubricant is calcium stearate, the double stearic acid acyls of ethylene
At least one of double stearates (PETS) of amine (EBS), pentaerythrite.
Preferably, antioxidant is antioxidant 1010 and irgasfos 168 in mass ratio 1：(1~2) the compounding antioxygen of composition
Agent；It is further preferred that antioxidant is antioxidant 1010 and irgasfos 168 in mass ratio 1：The compound antioxidant of 1 composition.
Preferably, nucleator is at least one of Sorbitol Nucleator, nucleator in organic phosphate class；It is further excellent
Choosing, nucleator is nucleator in organic phosphate class；Still further preferably, nucleator is organic phosphate nucleating agent NA-21.
A kind of preparation method of heat resistant transparent anti-impact PVDF/PP alloy materials, raw material is weighed by above-mentioned composition, mixing,
Extrusion, it is granulated, obtains heat resistant transparent anti-impact PVDF/PP alloy materials.
Preferably, twin-screw extrusion is extruded as, the parameter of double screw extruder is：One area's temperature is 180~200 DEG C；Two
Area's temperature is 185~205 DEG C；Three area's temperature are 190~210 DEG C；Four area's temperature are 185~205 DEG C；Five area's temperature be 185~
205℃；Six area's temperature are 185~205 DEG C；Seven area's temperature are 180~200 DEG C；Eight area's temperature are 180~200 DEG C；Head temperature
200~220 DEG C；Material residence time in double screw extruder is 0.5~1.5min；Vacuum -0.04~-0.06Mpa.
Present disclosure is described in further detail below by way of specific embodiment.
Above-mentioned raw material is weighed by mass percentage, 3~5min of high-speed stirred on homogenizer, reaches well mixed
Afterwards, well mixed raw material is put into double screw extruder, be granulated after melting extrusion.Wherein turn of double screw extruder
Speed is set as 300~600 revs/min, and each area's temperature setting of extruder is as follows：One area's temperature is 180~200 DEG C；Two area's temperature are
185~205 DEG C；Three area's temperature are 190~210 DEG C；Four area's temperature are 185~205 DEG C；Five area's temperature are 185~205 DEG C；Six
Area's temperature is 185~205 DEG C；Seven area's temperature are 180~200 DEG C；Eight area's temperature are 180~200 DEG C；Head temperature 200~220
℃；Material residence time in double screw extruder is 0.5~1.5min；Vacuum -0.04~-0.06Mpa.
The component and mass parts of embodiment 1 are as shown in table 1, and comparative example 1~3 as a comparison is also as shown in table 1.
The heat resistant transparent anti-impact PVDF/PP alloy materials formula of table 1 forms (mass parts)
| Raw material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 |
| HOPP | 100 | 100 | 97 | 97 |
| Kynoar | - | - | 3 | 3 |
| Transparent nucleater | - | 0.25 | - | 0.25 |
| Antioxidant 1010 | 0.20 | 0.20 | 0.20 | 0.20 |
| Irgasfos 168 | 0.20 | 0.20 | 0.20 | 0.20 |
| EBS | 0.30 | 0.30 | 0.30 | 0.30 |
Transparent nucleater in table 1 is the product of Japanese rising sun electrification company, and trade mark NA-21, outward appearance is powdered.
By obtained pellet in embodiment 1 and comparative example 1~3, corresponding batten is molded into according to testing standard, then 21
~25 DEG C, relative humidity is tested after being placed 24 hours in the environment of being 45~55%.
According to the light transmittance method of testings of ISO 14782, the printing opacity of test colour table (the long 50mm of specification × wide 50mm × thick 2mm)
Rate, numerical value is bigger, shows that the transparency of material is higher.
According to the glossiness method of testings of ISO 2813, colour table (the long 50mm of specification × wide 50mm) surface gloss, number are tested
Value is bigger, shows that the glossiness of material is higher.
The material properties test result of embodiment and comparative example is as shown in table 2.
The heat resistant transparent anti-impact PVDF/PP alloy material performances of table 2
| Test event | Testing standard | Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 |
| Light transmittance (%) | ISO 14782 | 84 | 89 | 90 | 92 |
| Glossiness (Gu) | ISO 2813 | 85 | 88 | 87 | 88 |
| Heat distortion temperature (DEG C) | ISO 75 | 100 | 115 | 107 | 118 |
| Melt flow rate (MFR) (g/10min) | ISO 1133 | 15 | 15 | 14 | 13 |
| Tensile strength (MPa) | ISO 527 | 32 | 40 | 34 | 42 |
| Elongation at break (%) | ISO 527 | >200 | >200 | >200 | >200 |
| Bending strength (MPa) | ISO 178 | 38 | 45 | 42 | 48 |
| Bending modulus (MPa) | ISO 178 | 1300 | 1600 | 1400 | 1800 |
| Izod notched impact strength (KJ/m2) | ISO 180 | 4.0 | 3.5 | 6.5 | 8.0 |
Compared with comparative example 1, comparative example 2 and comparative example 3 have a clear superiority：1) transparent nucleater or addition PVDF are added
Resin, transparency are significantly improved, but the transparent effect for adding PVDF is slightly better than addition transparent nucleater；2) add it is transparent into
Core agent or PVDF resins, the mechanical property of material can be improved, but add the mechanical property of transparent nucleater than addition PVDF trees
Fat is obviously improved；3) transparent nucleater or PVDF resins are added, the lustrous surface of material can be improved, but add transparent nucleater
Luster effect than addition PVDF resins it is slightly good；4) transparent nucleater or PVDF resins are added, the heat resistance of material can be improved
Can, but the heat distortion temperature for adding transparent nucleater is more notable than addition PVDF resin increases.A small amount of PVDF trees are added in PP
Fat, because PVDF resins have the fusing point and crystallization temperature higher than PP, so during PVDF/PP melt coolings crystallize,
PVDF first crystallizes than PP, and as temperature reduces, a small amount of PVDF fine crystals play a part of nucleus in PP crystallization process so that
PP crystallizes into epipole increase, causes the PP strands into same nucleus to reduce, and spherulitic growth is restricted, crystallite dimension compared with
It is small, visible light-transmissive is easily facilitated, therefore show as transparency raising.
Compared with comparative example 2 and comparative example 3, embodiment 1 is compounded using transparent nucleater and PVDF resins, transparency and power
Learn performance to be improved, illustrate that both transparent nucleater and PVDF resins have synergy.Because transparent nucleater and PVDF trees
Fat refines PP crystal grain size, and both compound addition and obtain tiny crystallite dimension than single addition, due to crystal grain
Particle diameter be less than visible ray wavelength, it is seen that light does not reflect, thus light transmittance improve become apparent from, while crystallize it is more perfect,
Therefore crystallinity, glossiness and heat distortion temperature accordingly improve.
Claims (8)
- A kind of 1. heat resistant transparent anti-impact PVDF/PP alloy materials, it is characterised in that：It is made up of the raw material of following mass percent： 88.5~98.3% acrylic resins, 1.0~10.0% polyvinylidene fluoride resins, 0.2~0.5% lubricant, 0.4~0.6% Antioxidant, 0.1~0.4% nucleator.
- A kind of 2. heat resistant transparent anti-impact PVDF/PP alloy materials according to claim 1, it is characterised in that：Polypropylene tree The MFR of fat is (3~50) g/10min.
- A kind of 3. heat resistant transparent anti-impact PVDF/PP alloy materials according to claim 1, it is characterised in that：Polyvinylidene fluoride The MFR of olefine resin is (0.5~5) g/10min.
- A kind of 4. heat resistant transparent anti-impact PVDF/PP alloy materials according to claim 1, it is characterised in that：Lubricant is In stearic acid, stearate, fatty acid amide, stearate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer It is at least one.
- A kind of 5. heat resistant transparent anti-impact PVDF/PP alloy materials according to claim 1, it is characterised in that：Antioxidant For antioxidant 1010 and irgasfos 168 in mass ratio 1：(1~2) compound antioxidant of composition.
- A kind of 6. heat resistant transparent anti-impact PVDF/PP alloy materials according to claim 1, it is characterised in that：Nucleator is At least one of Sorbitol Nucleator, nucleator in organic phosphate class.
- A kind of 7. preparation method of heat resistant transparent anti-impact PVDF/PP alloy materials, it is characterised in that：It is any by claim 1~6 Composition described in weighs raw material, mixes, and extrudes, and is granulated, obtains heat resistant transparent anti-impact PVDF/PP alloy materials.
- A kind of 8. heat resistant transparent anti-impact PVDF/PP alloy materials according to claim 1, it is characterised in that：It is extruded as double Screw Extrusion, the parameter of double screw extruder are：One area's temperature is 180~200 DEG C；Two area's temperature are 185~205 DEG C；3rd area Temperature is 190~210 DEG C；Four area's temperature are 185~205 DEG C；Five area's temperature are 185~205 DEG C；Six area's temperature are 185~205 ℃；Seven area's temperature are 180~200 DEG C；Eight area's temperature are 180~200 DEG C；200~220 DEG C of head temperature；Material is in twin-screw The residence time is 0.5~1.5min in extruder；Vacuum -0.04~-0.06Mpa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794890A (en) * | 2018-07-09 | 2018-11-13 | 广东圆融新材料有限公司 | PP/PVDF alloy materials and preparation method thereof |
| CN109880262A (en) * | 2019-03-01 | 2019-06-14 | 苏州宏裕千智能设备科技有限公司 | A kind of heat resistant transparent anti-impact PVDF/PP alloy material and preparation method thereof |
| CN110655710A (en) * | 2018-06-29 | 2020-01-07 | 合肥杰事杰新材料股份有限公司 | Scratch-resistant impact-resistant polypropylene material and preparation method thereof |
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| CN101585947A (en) * | 2008-05-21 | 2009-11-25 | 上海琢玥科技有限公司 | The preparation of low-cost fireresistant parting plastic complex film |
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