CN109467805A - A kind of low smell high durable roving glass fiber PP composite material and preparation method thereof - Google Patents
A kind of low smell high durable roving glass fiber PP composite material and preparation method thereof Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The invention belongs to field of polymer composite material, disclose a kind of low smell high durable Long Glass Fiber Reinforced PP Composite and preparation method thereof, the composite material, it is to be made of the raw material of following weight percents, the roving glass fiber of 10-60wt%, compound adsorbent 0.5-2wt%, weather-proof auxiliary agent 0.5-1wt%, compatilizer 1-5wt%, the polypropylene PP particle of 32-88wt%, compared with prior art, by using low smell compatilizer, method associated with compound adsorbent and smell processing unit, the smell and TVOC content of material are reduced to the greatest extent, prepared roving glass fiber particle dipping effect is good, product surface is floating fine few.Beneficial income of the invention is: prepared low smell high durable roving glass fiber PP composite material mechanical strength is high, smell is low, VOC content is few, weather resistance is excellent, long service life, and preparation method is simple and efficient, and can be applied in the environment complicated for operating condition, odor requirements are high.
Description
Technical field
The invention belongs to field of polymer composite material, specifically a kind of low smell high durable roving glass fiber polypropylene composite materials material
Material and preparation method thereof.
Background technique
Polypropylene has the characteristics that density is low, chemical stability is good and easy processing, is as second-biggest-in-the-world general-purpose plastics
A kind of plastics of great cost performance.But single polypropylene is asked there are easy to aging, weather resistance is bad, mechanical strength is not high
Topic, it is difficult to meet the performance requirement under complex working condition.Traditional method is that addition talcum powder, glass, antioxidant, toughener etc. are filled out
Material carries out engineering technology to it and is modified, to meet corresponding performance requirement.Long-fiber-reinforced thermoplastics (LFRT) conduct
A kind of tencel enhancing technology makes it have protrusion since remaining lengths of the fiber in product are greatly retained
Mechanical strength and heat resistance, while also reducing the anisotropic shrinkage of product, significantly reduce warpage, improve the ruler of product
Very little stability can be applied to the manufacture of auto parts, and can partially substitute automobile steel component parts, be that automobile realizes light-weighted
A kind of effective means.
In recent years, with the development of the social economy, automobile industry is higher and higher for the odor requirements of modified plastics.Tradition
Modified plastics, due to the addition of filler and auxiliary agent, unpleasant organic of generation that in the process of processing and using can be different degrees of
Volatile materials can generate human body uncomfortable when being applied to automotive upholstery or other closed environment.Therefore, stringent control
The organic volatile that automotive interior processed gives out becomes more and more important, it is only low distribute, low smell modified plastics is just able to satisfy
The demand for development in auto industry future.
Summary of the invention
The purpose of the present invention is to provide a kind of low smell high durable roving glass fiber PP composite material and preparation method thereof,
Resin may be implemented to the homogeneous impregnation of glass by modulation process parameter, while passing through compound adsorbent and smell processing dress
The method set, reduces the smell and VOC content of Long Glass Fiber Reinforced PP Composite, and prepared composite material is fine
Tie up it is secured with the interface cohesion of resin, volatilization less, smell it is low, long-term weatherability performance is good, is easy continuous production, with broader
Application prospect.
The invention discloses a kind of low smell high durable Long Glass Fiber Reinforced PP Composites, are by following weight percent
What the raw material of ratio was prepared, roving glass fiber 10-60wt%, compound adsorbent 0.5-2wt%, weather-proof auxiliary agent 0.5-1wt%, compatilizer
1-5wt% and polypropylene PP particle 32-88wt%.
Wherein, polypropylene PP particle is high-flowability polypropylene, and melt flow rate (MFR) is big under the conditions of 230 DEG C, 2.16Kg
In 50g/min.
Wherein, compound adsorbent is the composition of physical absorbent and chemosorbent, and the physical absorbent is more
The organophilic inorganic powder of microcellular structure, the chemosorbent are the modified chelating agent of hyperbranched polyether.
Preferably, physical absorbent is one kind of nano zine oxide after being surface-treated, titanium dioxide, porous aluminum silicon inorganic matter
Or several mixing, the chemosorbent are zinc ricinate or the modified chelating agent one or more mixing of hyperbranched polyether.
Wherein, weather-proof auxiliary agent is compound auxiliary agent, including primary antioxidant, auxiliary antioxidant and ultraviolet absorber form,
The primary antioxidant is Hinered phenols, and the auxiliary antioxidant is made of thioesters and phosphorous acid lipid, the purple
Outer absorbent is one kind of UV321 or LA-402F.
Preferably, primary antioxidant is antioxidant 1010, and the auxiliary antioxidant is irgasfos 168 and thio-2 acid
Both two (18) esters mixture.
Wherein, compatilizer is low smell maleic anhydride graft polypropylene, and grafting rate is in 0.8-1.2%.
The invention also discloses a kind of preparation methods of low smell high durable Long Glass Fiber Reinforced PP Composite, use
Above-mentioned formula, concrete technology preparation are as follows:
S1: roving glass fiber is drawn and is unfolded from the fiber roll on bracket, is introduced into preheating cabinet and is heated, pass through jockey pulley
It carries out pre-dispersed；
S2: will be introduced into temperature control impregnation mold by pre-dispersed roving glass fiber, and extruder is by polypropylene PP raw material and processing
After auxiliary agent mixing, it is squeezed into impregnation mold after vacuum extraction；
S3: the fibre bundle after dipping is towed on the pressure roller of roller being pulled into cooling trough cooling；
S4: it is granulated through the cooling fibre bundle of cooling trough by pelleter, and is put into the processing of smell processing unit, obtain low smell
High durable Long Glass Fiber Reinforced PP Composite.
The invention has the following advantages:
Compared with prior art, low smell high durable Long Glass Fiber Reinforced PP Composite provided by the invention overcomes poly- third
The performance deficiency of alkenyl body has given full play to the reinforcing effect and superiority of effectiveness of glass, has low smell, low VOC and Gao Nai
Characteristic is waited, operating condition complexity, the higher environment of odor requirements are suitable for.Provided low smell high durable long glass fiber reinforced composite wood
The melt impregnation preparation method of material removes the low molecular weight volatile substance in material using compound eliminating smell agent first, is making in particle
After the completion of grain, harmful low molecular weight volatile object in material is further removed by smell processing equipment, reduces the smell of material, two
Person combines, and significantly reduces the smell and VOC content of material.
Detailed description of the invention
Fig. 1 for the used device of preparation method of the present invention structural schematic diagram.
1: bracket, 2: roving glass fiber volume, 3: tension guide roller, 4: preheating oven, 5: temperature control impregnation mold, 6: extruder, 7: pressure
Roller, 8: cooling trough, 9: dragger, 10: pelleter, 11: smell processing unit.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.
Embodiment 1
The invention discloses a kind of low smell high durable roving glass fiber PP composite materials and preparation method thereof, wherein low smell is high
Weather-proof roving glass fiber PP composite material specifically:
Roving glass fiber 10-60wt%, compound adsorbent 0.5-2wt%, weather-proof auxiliary agent 0.5-1wt%, compatilizer 1-5wt% and polypropylene PP
Particle 32-88wt%.
Polypropylene is high-flowability polypropylene, and melt flow rate (MFR) is greater than 50g/min under the conditions of 230 DEG C, 2.16Kg.
Compound adsorbent is the composition of physical absorbent and chemosorbent, and physical absorbent is the parent of multi-cellular structure
The inorganic powder of organic matter, chemosorbent are the modified chelating agent of hyperbranched polyether, and (supplement composition ratio), physical absorbent is
One or more of mixing of nano zine oxide, titanium dioxide, porous aluminum silicon inorganic matter, the chemosorbent after surface treatment
For zinc ricinate or the modified chelating agent one or more mixing of hyperbranched polyether.
Weather-proof auxiliary agent is compound auxiliary agent, including primary antioxidant, auxiliary antioxidant and ultraviolet absorber composition, main antioxygen
Agent is Hinered phenols, and auxiliary antioxidant is made of thioesters and phosphorous acid lipid, and ultraviolet absorber is UV321 or LA-402F
One kind, it is preferred that primary antioxidant is antioxidant 1010, and auxiliary antioxidant is irgasfos 168 and thio-2 acid two (ten
Eight) both esters mixture.
Compatilizer is low smell maleic anhydride graft polypropylene, and grafting rate is in 0.8-1.2%.
Preparation equipment is as shown in Figure 1, a kind of low smell high durable long glass fiber-reinforced polypropylene melt impregnation of the present invention
Preparation method is completed using following device, and described device includes the bracket 1 for being equipped with several roving glass fibers volume 2, preheating cabinet 4,
The jockey pulley 3 being installed in preheating cabinet, the temperature control impregnation mold 5 being connected with 6 outlet end of extruder, is set to temperature control dipping former
Having the cooling trough 8 of 5 outlet ends, the pressure roller 7 being installed in cooling trough 8 is installed on the dragger 9 in 8 exit of cooling trough,
And it is installed on the pelleter 10 of 9 discharge end of dragger, it is installed on the smell processing unit 11 of 10 end of pelleter.
The preparation method is as follows:
S1: roving glass fiber is drawn and is unfolded from the fiber roll on bracket, is introduced into preheating cabinet and is heated, pass through jockey pulley
It carries out pre-dispersed；
S2: it will be introduced into temperature control impregnation mold by pre-dispersed roving glass fiber, extruder mixes PP raw material and processing aid
After conjunction, it is squeezed into impregnation mold after vacuum extraction；
S3: the fibre bundle after dipping is towed on the pressure roller of roller being pulled into cooling trough cooling；
S4: it is granulated through the cooling fibre bundle of cooling trough by pelleter, and is put into the processing of smell processing unit, obtain low smell
High durable Long Glass Fiber Reinforced PP Composite.
When it is implemented, the temperature in temperature control impregnation mold is 260-300 DEG C, the draw-down rate of glass is 10-35m/
min.Preferred temperature and draw-down rate can guarantee that master batch and processing aid are sufficiently mixed in the molten state, so that leaching
Stain material is uniform to the dipping of fiber.
Embodiment 2
The present embodiment carries out specifically refining analysis on the basis of embodiment 1, and present embodiment discloses a kind of low smell high durables
Roving glass fiber PP composite material and preparation method thereof, wherein the formula of composite material is as follows:
Roving glass fiber 10wt%, compound adsorbent 0.5wt%, weather-proof auxiliary agent 0.5wt%, compatilizer 1wt% and polypropylene PP particle
88wt%。
Wherein, compound adsorbent is made of titanium dioxide and zinc ricinate, and ratio 1:1, weather-proof auxiliary agent is by anti-oxidant
Agent 1010, antioxidant 168, thio-2 acid two (18) ester, LA-402F composition, each component ratio are as follows: 1:1:2:1 is compatible
Agent is homemade low smell maleic anhydride graft polypropylene, main that the side for waving agent and vacuum extraction is helped by addition low molecular weight
Method removes small molecule volatile matter therein, obtains low smell maleic anhydride graft polypropylene, and grafting rate gathers 0.8-1.2%
Propylene PP particle is high-flowability polypropylene, and melt flow rate (MFR) is greater than 50g/min under the conditions of 230 DEG C, 2.16Kg.
Roving glass fiber beam is drawn and is unfolded from the fiber roll 2 on bracket 1, is introduced into preheating cabinet 4, by preheating cabinet 4
Jockey pulley 3 carry out heating and it is pre-dispersed after, be introduced into impregnation mold 5, matched extruder 6 and 5 phase of temperature control impregnation mold
Even, extruder 6 squeezes into polypropylene PP particle, weather-proof auxiliary agent 0.5wt%, compound adsorbent 0.5wt% and compatilizer 1wt% to control
In warm impregnation mold 5, by the temperature of temperature control impregnation mold 5 be adjusted to 260 DEG C, the speed of dragger 9 be set as 15m/min.It will
Fibre bundle after dipping is directed through cooling trough 8 and is cooled down, and is granulated in pelleter 10, dry, through smell processing unit
11,120 DEG C are handled 3 hours, then obtaining roving glass fiber content is 10% low smell high durable long glass fiber reinforced PP composite material.
Embodiment 3:
Composite material described in the present embodiment is similar to preparation method to step 2, and wherein the formula of composite material is as follows:
Roving glass fiber 30wt%, compound adsorbent 1.5wt%, weather-proof auxiliary agent 0.5wt%, compatilizer 3wt% and polypropylene PP particle
65wt%。
Wherein, compound adsorbent is made of zinc oxide and the modified chelating agent of hyperbranched polyether, ratio 2:1.
Specific preparation method:
Long-fiber bundle is drawn and is unfolded from the fiber roll 2 on bracket 1, is introduced into preheating cabinet 4, by preheating cabinet 4
Power roller 3 carries out after heating and being pre-dispersed, is introduced into impregnation mold 5, and matched extruder 6 is connected with temperature control impregnation mold 5, squeezes
Polypropylene PP 65wt%, weather-proof auxiliary agent 0.5wt%, compound adsorbent 1.5wt% and compatilizer 3wt% are squeezed into temperature control and are soaked by machine 6 out
In stain mold 5, by the temperature of temperature control impregnation mold 5 be adjusted to 280 DEG C, the speed of dragger 9 be set as 20m/min.It will dipping
Fibre bundle afterwards is directed through cooling trough 9 and is cooled down, and is granulated in pelleter 10, dry, through smell processing unit 11,
120 DEG C are handled 3 hours, then must grow to glass fiber content is 30% low smell high durable long glass fiber reinforced PP composite material.
Embodiment 4:
Composite material described in the present embodiment is similar to preparation method to step 2, and wherein the formula of composite material is as follows:
Roving glass fiber 40wt%, compound adsorbent 2wt%, weather-proof auxiliary agent 1wt%, compatilizer 5wt% and polypropylene PP particle 52wt%.
Wherein, compound adsorbent is made of porous aluminum silicon inorganic matter and the modified chelating agent of hyperbranched polyether, ratio 1:2,
Weather-proof auxiliary agent is made of antioxidant 1010, antioxidant 168, thio-2 acid two (18) ester, LA-402F, each component ratio
Example are as follows: 2:3:3:2.
Specific preparation method:
Long-fiber bundle is drawn and is unfolded from the fiber roll 2 on bracket 1, is introduced into preheating cabinet 4, by preheating cabinet 4
Power roller 3 carries out after heating and being pre-dispersed, is introduced into impregnation mold 5, and matched extruder 6 is connected with temperature control impregnation mold 5, squeezes
Machine 6 squeezes into polypropylene PP 52wt%, weather-proof auxiliary agent 1wt%, compound adsorbent 2wt% and compatilizer 5wt% to temperature control dipping former out
In tool 5, by the temperature of temperature control impregnation mold 5 be adjusted to 290 DEG C, the speed of dragger 9 be set as 20m/min.After dipping
Fibre bundle is directed through cooling trough 8 and is cooled down, and is granulated in pelleter 10, dry, through smell processing unit 11,120
DEG C processing 3 hours, then obtain roving glass fiber content be 40% low smell high durable long glass fiber reinforced PP composite material.
Embodiment 5:
Composite material described in the present embodiment is similar to preparation method to step 2, and wherein the formula of composite material is as follows:
Roving glass fiber 60wt%, compound adsorbent 2wt%, weather-proof auxiliary agent 1wt%, compatilizer 5wt% and polypropylene PP particle 32wt%.
Wherein, compound adsorbent is made of porous aluminum silicon inorganic matter and the modified chelating agent of hyperbranched polyether, ratio 1:1.
Specific preparation method:
Long-fiber bundle is drawn and is unfolded from the fiber roll 2 on bracket 1, is introduced into preheating cabinet 4, by preheating cabinet 4
Power roller 3 carries out after heating and being pre-dispersed, is introduced into impregnation mold 5, and matched extruder 6 is connected with temperature control impregnation mold 5, squeezes
Machine 6 squeezes into polypropylene PP 32wt%, weather-proof auxiliary agent 1wt%, compound adsorbent 2wt% and compatilizer 5wt% to temperature control dipping former out
In tool 5, by the temperature of temperature control impregnation mold 5 be adjusted to 300 DEG C, the speed of dragger 9 be set as 35m/min.After dipping
Fibre bundle is directed through cooling trough 8 and is cooled down, and is granulated in pelleter 10, dry, through smell processing unit 11,130
DEG C processing 2 hours, then obtain roving glass fiber content be 60% low smell high durable long glass fiber reinforced PP composite material.
Embodiment 6
The present embodiment is injection moulded to obtain using the preparation-obtained composite material of embodiment 2-5 as experimental subjects to composite material
Standard batten is detected, and specific detection project includes: ash content, tensile strength, bending strength, bending modulus, impact strength, gas
Taste grade, TVOC, weatherability, used detection method are standard detecting method, and details are not described herein again.
Each embodiment item detection table of table 1
| Project | Testing standard | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Ash content (%) | ISO3451 | 9.8 | 31.2 | 39.9 | 59.2 | 30.8 | 40.2 | 59.6 |
| Tensile strength MPa | ISO 527/2 | 52 | 126 | 125 | 150 | 123 | 124 | 148 |
| Bending strength MPa | ISO 178 | 68 | 158 | 168 | 195 | 154 | 168 | 192 |
| Bending modulus MPa | ISO 178 | 1630 | 5800 | 8500 | 10800 | 5500 | 8400 | 10822 |
| Impact strength KJ/m2 | ISO 179-1 | 12 | 27 | 35 | 42 | 24 | 31 | 38 |
| Oder levels Class | VS-01.00-T-14004-A6- 2017 | 3 | 2.5 | 2.5 | 3 | 3.5 | 4 | 4 |
| TVOC µg/m3 | VS-01.00-T-14012-A3- 2017 | 2236 | 2320 | 2142 | 2980 | 5265 | 5613 | 6302 |
| Weatherability (xenon 1000h) | ISO-4982-2 | ΔE= 3.3 | ΔE= 3.5 | ΔE= 3.3 | ΔE= 3.2 | ΔE= 3.6 | ΔE= 4.2 | ΔE=4.1 |
Note: comparative example 1 are as follows: use 3 technique of embodiment, do not carry out the 30wt% long glass fiber-reinforced polypropylene composite wood of smell processing
Material injection forming obtains standard batten, and test obtains the mechanics and odor data of composite material.Comparative example 2 are as follows: use embodiment 4
Technique, the 40wt% Long Glass Fiber Reinforced PP Composite for not carrying out smell processing are injection moulded to obtain standard batten, test
To the mechanics and odor data of composite material.Comparative example 3 are as follows: use 5 technique of embodiment, do not carry out the 60wt% long of smell processing
Glass fiber reinforced polypropylene composite material is injection moulded to obtain standard batten, and test obtains the mechanics and odor data of composite material.
It is the mechanical property of the obtained low smell high durable long glass fiber reinforced PP composite material of embodiment 2,3,4,5 from table 1
Energy and oder levels.Comparing mechanical property all data can be seen that low smell high durable long glass fiber reinforced prepared by the present invention
The oder levels and TVOC content of PP composite material are below the common long glass fiber reinforced PP composite material for not carrying out smell processing,
Excellent in mechanical performance, smell be small, weatherability it is found that melt impregnation preparation method of the present invention can obtain for 1 data of consolidated statement
Good long glass fiber reinforced PP composite material, has a extensive future.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of low smell high durable Long Glass Fiber Reinforced PP Composite, which is characterized in that be by following weight percents
Raw material be prepared, roving glass fiber 10-60wt%, compound adsorbent 0.5-2wt%, weather-proof auxiliary agent 0.5-1wt%, compatilizer 1-
5wt% and polypropylene PP particle 32-88wt%.
2. a kind of low smell high durable Long Glass Fiber Reinforced PP Composite as described in claim 1, which is characterized in that institute
The polypropylene PP particle stated is high-flowability polypropylene, and melt flow rate (MFR) is greater than 50g/ under the conditions of 230 DEG C, 2.16Kg
min。
3. a kind of low smell high durable Long Glass Fiber Reinforced PP Composite as described in claim 1, which is characterized in that institute
The compound adsorbent stated is the composition of physical absorbent and chemosorbent, and the physical absorbent is multi-cellular structure
Organophilic inorganic powder, the chemosorbent are the modified chelating agent of hyperbranched polyether.
4. a kind of low smell high durable Long Glass Fiber Reinforced PP Composite as claimed in claim 3, which is characterized in that institute
The physical absorbent stated is one or more of mixing of nano zine oxide, titanium dioxide, porous aluminum silicon inorganic matter after surface treatment,
The chemosorbent is zinc ricinate or the modified chelating agent one or more mixing of hyperbranched polyether.
5. a kind of low smell high durable Long Glass Fiber Reinforced PP Composite as described in claim 1, which is characterized in that institute
The weather-proof auxiliary agent stated is compound auxiliary agent, including primary antioxidant, auxiliary antioxidant and ultraviolet absorber composition, the master resist
Oxygen agent is Hinered phenols, and the auxiliary antioxidant is made of thioesters and phosphorous acid lipid, and the ultraviolet absorber is
One kind of UV321 or LA-402F.
6. a kind of low smell high durable Long Glass Fiber Reinforced PP Composite as claimed in claim 5, which is characterized in that institute
The primary antioxidant stated is antioxidant 1010, and the auxiliary antioxidant is irgasfos 168 and thio-2 acid two (18) ester
The two mixture.
7. a kind of low smell high durable Long Glass Fiber Reinforced PP Composite as described in claim 1, which is characterized in that institute
The compatilizer stated is low smell maleic anhydride graft polypropylene, and grafting rate is in 0.8-1.2%.
8. a kind of preparation method of low smell high durable Long Glass Fiber Reinforced PP Composite, which is characterized in that use right
It is required that formula described in 1-7 any one, concrete technology preparation is as follows:
S1: roving glass fiber is drawn and is unfolded from the fiber roll on bracket, is introduced into preheating cabinet and is heated, pass through jockey pulley
It carries out pre-dispersed；
S2: will be introduced into temperature control impregnation mold by pre-dispersed roving glass fiber, and extruder is by polypropylene PP raw material and processing
After auxiliary agent mixing, it is squeezed into impregnation mold after vacuum extraction；
S3: the fibre bundle after dipping is towed on the pressure roller of roller being pulled into cooling trough cooling；
S4: it is granulated through the cooling fibre bundle of cooling trough by pelleter, and is put into the processing of smell processing unit, obtain low smell
High durable Long Glass Fiber Reinforced PP Composite.
Priority Applications (1)
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| CN111533467A (en) * | 2020-06-09 | 2020-08-14 | 巨石集团有限公司 | Impregnating compound for glass fiber direct roving and preparation method, product and application thereof |
| CN112266531A (en) * | 2020-09-24 | 2021-01-26 | 句容市百事特复合材料有限公司 | Low-odor long fiber reinforced polypropylene granule composition and preparation method thereof |
| CN112321938A (en) * | 2020-11-18 | 2021-02-05 | 太仓市华鼎塑料有限公司 | Low-emission PP material and preparation method thereof |
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