CN112608413A - Maleic anhydride grafted polypropylene with low free maleic anhydride content and low-emission glass fiber reinforced polypropylene composite material prepared from maleic anhydride grafted polypropylene - Google Patents
Maleic anhydride grafted polypropylene with low free maleic anhydride content and low-emission glass fiber reinforced polypropylene composite material prepared from maleic anhydride grafted polypropylene Download PDFInfo
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 title claims abstract description 65
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 51
- 239000003365 glass fiber Substances 0.000 title claims abstract description 51
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 43
- -1 polypropylene Polymers 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- 229920005633 polypropylene homopolymer resin Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000011361 granulated particle Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Manufacturing & Machinery (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides maleic anhydride grafted polypropylene with low free maleic anhydride content and a low-emission glass fiber reinforced polypropylene composite material prepared from the maleic anhydride grafted polypropylene. In the maleic anhydride grafted polypropylene, the free maleic anhydride which is not successfully grafted accounts for less than 10 percent of the total mole content of the maleic anhydride in the maleic anhydride grafted polypropylene. The maleic anhydride grafted polypropylene provided by the invention has low free maleic anhydride content, and can obviously improve the emission performance of the final glass fiber reinforced polypropylene composite material. The maleic anhydride grafted polypropylene is used as a compatilizer, special extrusion processing equipment and processing technology are not required to be equipped, the extrusion process is simple and convenient, and the compatilizer has the characteristics of continuity and effectiveness, has a good emission effect on extruded and granulated particles and final injection molded parts, and has good grades in the aspects of smell, TVOC and haze.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to maleic anhydride grafted polypropylene with low free maleic anhydride content and a low-emission glass fiber reinforced polypropylene composite material prepared from the maleic anhydride grafted polypropylene.
Background
With the continuous improvement of the living standard of people, the health problem is more and more emphasized by people, so that higher requirements are put forward on the air quality of the living environment, the working environment and the environment in the vehicle, which are closely related to the life. In order to improve the air quality of the environment inside the vehicle, numerous host plants have purposefully issued the control requirements of the emission (including odor, VOC, haze) of various interior part assemblies.
With the proposal of the concept of light weight of automobiles, more and more plastic parts are used for interior and exterior parts of automobiles, wherein the glass fiber reinforced polypropylene material is widely applied to automobiles, such as skylight frames, instrument panel frameworks, engine covers, bumper brackets and other parts, due to the excellent comprehensive mechanical property of the glass fiber reinforced polypropylene material. The requirement for the automotive interior trim part to be subjected to emission control is higher and higher, so that higher requirements are put on the glass fiber filled polypropylene material. Because the glass fiber is not compatible with the polypropylene resin, a compatilizer with a proper proportion needs to be added into the glass fiber reinforced polypropylene composite material, and the most common compatilizer is maleic anhydride grafted polypropylene, so that the viscosity between the glass fiber and the polypropylene material can be improved, and the mechanical property of the material is improved. However, the maleic anhydride grafted polypropylene product of the melt grafting method of the conventional method has a higher proportion of the maleic anhydride monomer in a free state which is not grafted successfully (the maleic anhydride in the free state which is not grafted successfully accounts for 25-80% of the total mole content of the maleic anhydride (the maleic anhydride in the free state + the maleic anhydride which is grafted successfully effectively) in the maleic anhydride grafted polypropylene), and the maleic anhydride monomer in the free state has strong volatility on one hand, and on the other hand, can be heated to induce the oxidation of the polypropylene chains in the extrusion processing process, so that more volatile micromolecules are formed, and the volatility of the whole material is influenced. Although some patents mention reducing the residual maleic anhydride content by some technical means to improve the final odor, such as CN104193903A using combination of introducing a second grafting monomer and a premixing process of a reaction kettle, CN105440217A using staged addition of a high temperature initiator and a low temperature initiator, and CN101591416A combining melt grafting and solid phase grafting can play a role in reducing the residual maleic anhydride, and can improve the final odor to some extent. However, the following disadvantages are present compared to the solution grafting method mentioned in this patent: these patents all use a melt grafting method, the reaction temperature is higher than the melting point of polypropylene, during the melting process, a certain amount of free radicals are generated, which affects the emitting odor of the final fiber reinforced polypropylene material (the odor is not the odor of maleic acid, but the odor generated by the chain breaking of polypropylene molecular chains), and the thermal stability of maleic anhydride grafting is not high enough, so that the grafted maleic anhydride is easily thermally removed during the secondary processing heating process, which affects the effect of the compatibilizer.
In order to solve the above problems and reduce the emission of the glass fiber reinforced polypropylene, the glass fiber reinforced polypropylene is usually devolatilized by a method including a devolatilization method, an adsorption method, and a baking method. Although all three of these methods have some effect on reducing emission, there are significant drawbacks. The removing method has the defects that the requirements on extrusion equipment and a process are high, and a special extracting agent is prepared in advance and a special vacuum device is required to be equipped; the adsorption method has the defects that an adsorbent needs to be added in the processing process, but the mechanical property is reduced to a certain extent after the adsorbent is added; the baking method has the defects that special baking equipment is required, only small molecular substances on the surfaces of particles can be removed, the residual free maleic anhydride in the particles cannot be removed by baking, and the residual free maleic anhydride is released again after being injection molded into a finished piece.
In the prior art, a solution grafting method is adopted to prepare maleic anhydride grafted polypropylene, but the grafting conversion rate is not high, so that a large amount of maleic anhydride raw materials are required to be added to reach the required grafting rate, and the free maleic anhydride content in a crude product is high. Although the maleic anhydride is removed by vacuum drying in the subsequent process, the free maleic anhydride proportion is still about 15%.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of maleic anhydride grafted polypropylene with low free maleic anhydride content.
Another object of the present invention is to provide a low emission glass fiber reinforced polypropylene composite.
The invention also aims to provide a preparation method of the low-emission glass fiber reinforced polypropylene composite material.
The invention also aims to provide application of the low-emission glass fiber reinforced polypropylene composite material.
The above purpose of the invention is realized by the following technical scheme:
a method for preparing maleic anhydride grafted polypropylene is carried out by adopting a solution grafting method, wherein the grafting process is carried out under a supercritical medium, and after crude maleic anhydride grafted polypropylene is separated out, vacuum drying is adopted for devolatilization treatment, so that free maleic anhydride which is not successfully grafted in a maleic anhydride grafted polypropylene product accounts for less than 10% of the total mole content of maleic anhydride in the maleic anhydride grafted polypropylene.
The inventor finds that the free maleic anhydride is a main source of a volatile substance in the maleic anhydride grafted polypropylene, the invention provides a novel solution grafting method for preparing the maleic anhydride grafted polypropylene, the solution grafting process is carried out in a supercritical medium, the grafting efficiency can be higher, and the content of the free maleic anhydride which is not successfully grafted in the maleic anhydride grafted polypropylene product can be reduced to a lower level by matching with the subsequent vacuum drying treatment. Therefore, the maleic anhydride grafted polypropylene can better improve the emission of the glass fiber reinforced polypropylene composite material. Under the method of the invention, the grafting conversion rate is more than 90 percent, so the content of free maleic anhydride in the crude product is lower, and the content of free maleic anhydride in the final product after post-treatment can be at a lower level than that of the prior solution grafting method.
In the maleic anhydride grafted polypropylene prepared by the method, the grafting rate is more than 0.8 percent. The graft ratio is preferably 1.1% or more.
More preferably, in the maleic anhydride grafted polypropylene, the maleic anhydride in a free state which is not successfully grafted accounts for less than 5% of the total mole content of the maleic anhydride in the maleic anhydride grafted polypropylene.
The preparation method of the maleic anhydride grafted polypropylene is preferably carried out by adopting a solution grafting method. Specifically, the method comprises the following steps:
adding polypropylene and xylene into a reaction kettle, adding maleic anhydride monomer, adding a xylene solution of benzoyl peroxide, and filling CO2Discharging the air in the reaction kettle, and injecting CO again2Raising the temperature to make the pressure reach more than 8 MPa; after the reaction is finished, adding acetone to separate out a crude maleic anhydride grafted polypropylene product; and (3) after washing treatment, drying the mixture in vacuum at the temperature of 75-120 ℃ to constant weight, wherein the vacuum degree is not lower than-0.08 MPa, and obtaining the final maleic anhydride grafted polypropylene product.
A low-emission glass fiber reinforced polypropylene composite material comprises the following components in parts by weight:
the compatilizer is maleic anhydride grafted polypropylene prepared by the preparation method.
The maleic anhydride grafted polypropylene prepared by the preparation method of the invention replaces the conventional maleic anhydride grafted polypropylene, and the content of free maleic anhydride in the maleic anhydride grafted polypropylene is far lower than that of the conventional maleic anhydride grafted polypropylene, so that the emission performance of the final glass fiber reinforced polypropylene composite material can be obviously improved.
The polypropylene resin may be homo-polypropylene or co-polypropylene. The melt flow rate of the polypropylene resin is 0.1-180 g/10min under the test condition of 230 ℃ multiplied by 2.16 kg.
Preferably, the polypropylene resin is homopolypropylene.
More preferably, the homopolypropylene resin is a homopolypropylene synthesized by a metallocene catalyst.
The glass fibers may be glass fibers that are conventionally used as fillers, and more preferably, the glass fibers are preferably chopped alkali-free glass fibers.
Preferably, the average length of the glass fiber is 5-20 μm;
the other functional aids include one or more of antioxidants, light stabilizers, scratch resistance agents, lubricants, colorants, foaming agents, surfactants, plasticizers, flame retardants, antistatic aids, antimicrobial aids, nucleating agents, which are considered desirable by those skilled in the art.
The preparation method of the low-emission glass fiber reinforced polypropylene composite material can adopt the following methods 1) or 2):
1) preparing the components into a premix, and then melting and extruding the premix;
2) preparing the components except the glass fiber into premix, feeding from a main feeding port of an extruder, feeding the glass fiber from a side feeding port, and performing melt extrusion to obtain the glass fiber premix.
Preferably, the melt extrusion conditions are: the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 190-.
The melt extrusion is preferably carried out by adopting a double-screw extruder, and the length-diameter ratio of the double-screw extruder is preferably 36: 1-56: 1.
The low-emission glass fiber reinforced polypropylene composite material is applied to the preparation of automotive upholstery.
Compared with the prior art, the invention has the following beneficial effects:
the maleic anhydride grafted polypropylene prepared by the preparation method provided by the invention has low free maleic anhydride content, and can be used for replacing the conventional maleic anhydride grafted polypropylene, so that the emission performance of the final glass fiber reinforced polypropylene composite material can be obviously improved. The maleic anhydride grafted polypropylene is used as a compatilizer, special extrusion processing equipment and processing technology are not required, the extrusion process is simple and convenient, and the processing and the production process are the same as those of the conventional glass fiber reinforced polypropylene material; the off-line baking equipment is not required, the energy consumption for baking materials can be saved, the continuous and effective characteristics are achieved, the good emission effect is achieved for the extruded and granulated particles or the final injection molded parts, and the good grades are achieved in the aspects of smell, TVOC and haze.
Detailed Description
The present invention will be described in further detail with reference to specific examples and comparative examples, but the present invention is not limited to the examples.
In the examples, the starting materials not specifically mentioned are all conventional commercial products.
The polypropylene copolymer is 25g/min polypropylene copolymer under the conditions that the test temperature is 230 ℃ and the weight of the test weight is 2.16kg, and the crystallinity is 35.6 percent;
homo-polypropylene 1: the homo-polypropylene catalyzed by the Ziegler-Natta catalyst used was a homo-polypropylene catalyzed and synthesized by the Ziegler-Natta catalyst at 25g/min under the conditions that the test temperature was 230 ℃ and the weight of the test weight was 2.16kg, and the crystallinity was 52.4%.
Homo-polypropylene 2: the homopolymerized polypropylene catalyzed by the metallocene catalyst is homopolymerized polypropylene which is synthesized by metallocene catalysis at 25g/min under the conditions that the testing temperature is 230 ℃ and the weight of a testing weight is 2.16kg, and the crystallinity is 52.2 percent;
glass fiber: chopped alkali-free glass fibers, ECS301CL, Chongqing International composite materials, Inc., diameter 10 μm, length 3 mm;
selected maleic anhydride grafted polypropylene a: BONDYRAM 1001CN available from Polyram, the effective grafting rate is 1.15%, and the free maleic anhydride mole ratio is 25%;
selected maleic anhydride grafted polypropylenes B: self-made, the effective grafting rate is 1.15 percent, and the free maleic anhydride accounts for 9 percent in mole;
selected maleic anhydride grafted polypropylene C: self-made, the effective grafting rate is 1.15 percent, and the free maleic anhydride accounts for 3 percent;
selected maleic anhydride grafted polypropylene D: self-made, the effective grafting rate is 1.15 percent, and the free maleic anhydride accounts for 14 percent;
selected maleic anhydride grafted polypropylene E: self-made, the effective grafting rate is 1.15 percent, and the free maleic anhydride accounts for 50 percent;
the preparation method of the maleic anhydride grafted polypropylene B comprises the following steps:
adding a certain amount of PP and xylene into a high-pressure reaction kettle, stirring and heating to about 110 ℃, adding Maleic Anhydride (MAH) monomer, wherein the weight ratio of the maleic anhydride monomer to the PP is 0.01276/1, adding a xylene solution of Benzoyl Peroxide (BPO) when the materials are completely dissolved, and filling high-purity CO2Discharging air from the autoclave for 10min, closing the outlet valve, and injecting CO with a pressure pump2Then, the temperature was raised to 125 ℃ to bring the pressure to 10 MPa. After reacting for 3h, cooling to about 50 ℃, adding acetone, and separating out a product. And (3) after the product is subjected to suction filtration and washing, placing the product in an extraction device, eluting the product with acetone for 24 hours, and then performing vacuum drying at 75 ℃ to constant weight, wherein the vacuum degree is controlled to be-0.085 MPa, so as to obtain the final maleic anhydride grafted polypropylene self-made product. The graft conversion was 91.3%.
The preparation method of the maleic anhydride grafted polypropylene C comprises the following steps:
adding a certain amount of PP and xylene into a high-pressure reaction kettle, stirring and heating to about 110 ℃, adding Maleic Anhydride (MAH) monomer, wherein the weight ratio of the maleic anhydride monomer to the PP is 0.01276/1, and completely dissolving the materialsAdding xylene solution of Benzoyl Peroxide (BPO), and charging high purity CO2Discharging air from the autoclave for 10min, closing the outlet valve, and injecting CO with a pressure pump2Then, the temperature was raised to 125 ℃ to bring the pressure to 10 MPa. After reacting for 3h, cooling to about 50 ℃, adding acetone, and separating out a product. And (3) after the product is subjected to suction filtration and washing, placing the product in an extraction device, eluting the product with acetone for 24 hours, and then performing vacuum drying at 120 ℃ to constant weight, wherein the vacuum degree is controlled to be-0.085 MPa, so as to obtain the final maleic anhydride grafted polypropylene self-made product. The graft conversion was 91.3%.
The preparation method of the maleic anhydride grafted polypropylene D comprises the following steps:
adding a certain amount of PP and xylene into a high-pressure reaction kettle, stirring and heating to about 110 ℃, adding Maleic Anhydride (MAH) monomer, wherein the weight ratio of the maleic anhydride monomer to the PP is 0.01626/1, adding a xylene solution of Benzoyl Peroxide (BPO) when the materials are completely dissolved, and then heating to the reaction temperature of 125 ℃ to ensure that the pressure reaches 10 MPa. After reacting for 3h, cooling to about 50 ℃, adding acetone, and separating out a product. And (3) after the product is subjected to suction filtration and washing, placing the product in an extraction device, eluting the product with acetone for 24 hours, and then performing vacuum drying at 120 ℃ to constant weight, wherein the vacuum degree is controlled to be-0.085 MPa, so as to obtain the final maleic anhydride grafted polypropylene self-made product. The graft conversion was 71.9%.
The preparation method of the maleic anhydride grafted polypropylene E comprises the following steps:
uniformly premixing certain amounts of PP, Maleic Anhydride (MAH) monomer and Benzoyl Peroxide (BPO), wherein the weight ratio of the maleic anhydride monomer to the PP is 0.02354/1, and carrying out melt blending through a single-screw extruder under the conditions of: the temperature of the melting section is 170 ℃, the temperature of the reaction section and the output end is 200 ℃, and the retention time is 150 s. The graft conversion was 50.0%.
The effective grafting rate, grafting conversion rate and free maleic anhydride determination method are tested by an acid-base titration method commonly used in the field. Accurately weighing 1g of the product, adding 50ml of dimethylbenzene, heating for dissolving, cooling, adding 10ml of 0.1mol/L KOH-ethanol solution, refluxing in a water bath at 90 ℃ for 20min, cooling to room temperature, and adding a phenolphthalein indicator. And (5) calibrating the standard solution to the end point by using 0.1mol/L HCl standard solution, and simultaneously carrying out a blank test.
The effective grafting ratio is calculated according to the following formula:
effective graft ratio ═ V0-V1) X N × 49/10W × 100%, wherein:
V0-the volume of HCl standard solution consumed in the blank experiment, ml;
V1-the volume of HCl standard solution consumed by the sample, ml;
n is the concentration of HCl standard solution, mol/L;
w-sample mass, g;
49-1/2 g/mol of molar mass of MAH.
The graft conversion was calculated as follows: maleic anhydride molar content with successful grafting/total maleic anhydride molar content added
Free maleic acid ratio (mole content of free maleic anhydride in maleic anhydride grafted polypropylene/mole content of all maleic anhydride in maleic anhydride grafted polypropylene)
Antioxidant: hindered phenol main antioxidant and phosphite ester auxiliary antioxidant.
Light stabilizer: hindered amine light stabilizers;
colorant: and (4) black color master batch.
Performance testing
Tensile properties were performed according to ISO 527-2019; bending performance was performed according to ISO 178-2019; impact performance was performed according to ISO 180-2019; density was performed according to ISO 1183-2019; odor performance is performed according to Volkswagen PV 3900-2019; TVOC is tested by the 10L bag method according to VS-00.28-L-06017(2018) standard; haze test the haze test was performed according to ISO 6452-2007 weight method.
Examples 1 to 7 and comparative examples 1 to 3
According to the formula of table 1, examples 1 to 6 and comparative examples 1 to 3 were prepared, specifically including the following steps:
and (3) dry-mixing the components except the glass fiber in a high-speed mixer for 5-15 min to prepare a premix, adding the premix into a double-screw extruder from a main screw feeding port, adding the glass fiber into the double-screw extruder from the middle side of a screw to a feeding port, and performing melt extrusion, granulation and drying to obtain the finished product.
Example 7 was prepared according to the formulation of table 1, with the following specific preparation steps:
mixing the components in a high-speed mixer for 1-3 min at a high speed, and uniformly mixing to obtain a premix; and (3) putting the premix into a main feeding port of a double-screw extruder for melt extrusion, and granulating and drying after melt extrusion to obtain a finished product.
In each example, the conditions for melt extrusion were: the temperature of the first zone is 100 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 220 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the ninth zone is 220 ℃, and the rotating speed of the main engine is 500 r/min; the length-diameter ratio of the twin-screw extruder is 40: 1.
In the examples and comparative examples, the respective materials were used in parts by weight.
TABLE 1
As can be seen from Table 1, comparing examples 1-3 with each other, it can be seen that the homo-polypropylene is selected as the matrix, and the matrix has better emission performance than the co-polypropylene, because the homo-polypropylene has higher crystallinity, and because the crystal structure is denser, the small molecule residual space is limited, and the emission performance is better relatively. In example 3, the metallocene catalyst homo-polypropylene has a narrow molecular weight distribution and better emission performance than the conventional Ziegler-Natta catalyst homo-polypropylene; in general contrast, the selection of the matrix does not have much influence on the mechanical properties of the glass fiber filling material. Comparing examples 3-4 with comparative examples 1 and 2, it can be seen that the lower the free maleic anhydride ratio, the better the emission performance (including odor, TVOC and haze) and the more significant the impact, without much impact on mechanics. However, the prior solution grafting method cannot obtain the maleic anhydride grafted polypropylene with low free maleic anhydride. As can be seen from comparative examples 1 and 3, the maleic anhydride grafted polypropylene prepared by the melt grafting method has high free maleic anhydride content and much lower emission than the product prepared by the solution grafting method. Comparing example 3 with examples 5-6, it can be seen that the dispersion performance effect is better within the required component types, component ratios and process ranges. Comparing example 3 with example 7, it can be seen that the two glass fiber feeding modes have little effect on emission performance, and the mechanical properties are less for the main feeding mode versus the side feeding mode due to the longer screw shear experienced by the glass fibers in the main feeding processing mode.
Claims (10)
1. A preparation method of maleic anhydride grafted polypropylene is carried out by adopting a solution grafting method, and is characterized in that the grafting process is carried out under a supercritical medium, and after crude maleic anhydride grafted polypropylene is separated out, vacuum drying is adopted for devolatilization treatment, so that free maleic anhydride which is not successfully grafted in a maleic anhydride grafted polypropylene product accounts for less than 10% of the total mole content of maleic anhydride in the maleic anhydride grafted polypropylene.
2. The method according to claim 1, wherein the maleic anhydride-grafted polypropylene contains maleic anhydride in an amount of less than 5% by mole based on the total molar amount of maleic anhydride in the maleic anhydride-grafted polypropylene in a free state without being grafted successfully.
3. The process for producing maleic anhydride-grafted polypropylene according to claim 1, comprising the steps of:
adding polypropylene and xylene into a reaction kettle, adding maleic anhydride monomer, adding a xylene solution of benzoyl peroxide, and filling CO2Discharging the air in the reaction kettle, and injecting CO again2Raising the temperature to make the pressure reach more than 8 MPa; after the reaction is finished, adding acetone to separate out a crude maleic anhydride grafted polypropylene product; after washing treatment, vacuum drying at 75-120 ℃ to constant weight, wherein the vacuum degree is not lower than-0.08 MPa, and finally obtaining the maleic anhydride grafted polypropylene product。
4. The low-emission glass fiber reinforced polypropylene composite material is characterized by comprising the following components in parts by weight:
the compatilizer is maleic anhydride grafted polypropylene prepared by the preparation method of any one of claims 1 to 3.
5. The low-emission glass fiber reinforced polypropylene composite material of claim 4, wherein the polypropylene resin is homo-polypropylene.
6. The low-emission glass fiber reinforced polypropylene composite material of claim 5, wherein the homo-polypropylene resin is a homo-polypropylene synthesized by a metallocene catalyst.
7. The low emission glass fiber reinforced polypropylene composite of claim 4, wherein the glass fibers are chopped alkali-free glass fibers.
8. The low-emission glass fiber reinforced polypropylene composite material as claimed in claim 4 or 7, wherein the average length of the glass fiber is 5 to 20 μm.
9. The method for preparing the low-emission glass fiber reinforced polypropylene composite material as claimed in claim 4, wherein the following method 1) or 2) is adopted:
1) preparing the components into a premix, and then melting and extruding the premix;
2) preparing the components except the glass fiber into premix, feeding from a main feeding port of an extruder, feeding the glass fiber from a side feeding port, and performing melt extrusion to obtain the glass fiber premix.
10. Use of the low-emission glass fiber reinforced polypropylene composite material according to any one of claims 4 to 7 in the preparation of automotive interior parts.
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