CN106854310A - A kind of preparation method of PP composite material - Google Patents
A kind of preparation method of PP composite material Download PDFInfo
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- CN106854310A CN106854310A CN201710027940.3A CN201710027940A CN106854310A CN 106854310 A CN106854310 A CN 106854310A CN 201710027940 A CN201710027940 A CN 201710027940A CN 106854310 A CN106854310 A CN 106854310A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
- B29C2948/9258—Velocity
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- 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
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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
- C08L2201/08—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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
- C08L2205/242—Beta spherulite nucleating agents
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Abstract
The present invention relates to a kind of preparation method of PP composite material, the method is made up of polypropylene, bulking agent, glass fibre, nucleator, antioxidant of two-step method, first induce polypropylene that crystal transfer occurs with nucleator first, then the method that is further enhanced is combined therewith with glass fibre again, solve and directly mixed polypropylene with nucleator and fiber in conventional method, because glass fibre is used as a kind of introducing of exogenous impurity so that nucleator can not effectively play the problem of the effect of its regulation and control crystalling propylene behavior.The present invention effectively combines nucleator regulation and control and glass fiber reinforcement, and collaboration improves the combination property of PP composite material, and not only comprehensive mechanical property is good for the PP composite material obtained by the method for the invention, and heat endurance is high.Meanwhile, the base glass fiber for being used is cheap and easy to get, the process is simple of the twin-screw extrusion for being used, low cost, is easy to implement large-scale production and applies.
Description
Technical field
The present invention relates to a kind of preparation method of PP composite material, and in particular to a kind of glass fibre and nucleator are common
With the modified method for preparing PP composite material.
Background technology
Polypropylene (PP) as one of five big general-purpose plastics, with inexpensive, density is low, easy processing and good mechanical performance
The advantages of, with the continuous expansion of range of application, it has been applied to the fields such as Aero-Space, packaging for foodstuff, automobile.However, PP
Also there are some defects, for example：Shrinkage factor high, toughness are low and easily aging, more sensitive to light and heat and relatively low at low temperature
Impact strength, these all limit further applying for it.
In order to expand the range of application of PP, researcher develops many methods and carrys out modified polypropene, such as：Add filler or
Nucleator.Polypropylene is a kind of polycrystalline state polymer, common and main crystal formation be monoclinic system α-crystal formation and hexagonal crystal system β-
Crystal formation.In the structure of α-crystal formation, platelet be from spherocrystal center it is radially multidirectional to surrounding radioactivity grow, this causes that it has
Rigidity higher, but its toughness is weaker；Comparatively speaking, in beta-crystal platelet by spherocrystal center or it is parallel be combined into beam, then
Outwards branched to grow or helically to outgrowth, branched again afterwards, this structure imparts its good toughness.β-PP exist
Thermodynamically belong to metastable state, be hardly formed under field conditions (factors), accordingly, it would be desirable to can be formed by some external force
Beta-crystal.At present, the formation of beta-crystal mainly has three kinds of methods：Orient to form beta-crystal, shearing with thermograde as power
Induction crystallization and addition nucleating agent.In these methods, it is a kind of raising poly- third to adding nucleating agent to have been found in PP
The most direct effective method of alkene toughness of material, while not influenceing its strength and stiffness.
The beta nucleater (gamma-quinacridinelone (E3B)) that the first is found is Leugering in (Die in 1967
Makromolekulare Chemie,1967,109(1):204-216) report, but because the color of gamma-quinacridinelone is red
Color, this limits its application in true qualities or light color article, and the nucleator synthesis technique is complicated, and cost of material is high.Recently,
It is efficient beta nucleater that calcium pimelate and N, N '-dicyclohexyl -2,6- aphthalimides are reported in document；However, β-PP
Formation is generally required to carry out at high temperature, therefore analysis is easily formed in the molding process with calcium pimelate as nucleator
Go out thing and have a strong impact on the service efficiency and quality of item of PP；Additionally, N, N '-dicyclohexyl -2,6- aphthalimide nucleators
As a kind of organic molecule, there is good dissolubility in polypropylene, and fusing point is higher, and these are all beneficial to the nucleator
Range of application.
In order to further reduce the cost of amide-type nucleator, the induction crystalline rate of nucleator, Chinese patent (Shen are improved
One kind number please 200910062705.5) be disclosed amide-type beta nucleater is attached on nano silicon and a kind of β has been obtained
Nucleator, acid amides used is N, N '-dicyclohexyl terephthalamide or N, N '-dicyclohexyl -2,6- aphthalimides.Should
Method is successfully supported on nano-silica surface by by amide-type, improves the contact surface of amide-type nucleator and PP
Product, so as to improve nucleation efficiencies.
Documents (Macromolecules 2006,39 (17):1,4- phenylenes-bis- acyls are reported in 5760-5767)
As a result amine show that it can effectively induce PP to crystallize as beta crystal as nucleator.
Documents (Journal of Polymer Science Part B:Polymer Physics 2009,47
(3):When concentration 314-325) reported when TMB-5 amide-types nucleator in PP matrixes is critical concentration, the crystalline phase of formation
Collectively formed by α and β two-phases；When nucleation agent content is higher than critical concentration, it is thin that nucleator forms micron-sized crystal in PP
Rod induces PP to be grown with the direction on vertical nucleator surface, has ultimately generated the β spherocrystals of ellipsoid, and beta crystal nucleation rate and knot
The change that brilliant degree is produced as TMB-5 concentration increases.
Report in documents (Journal of Applied Polymer Science, 2013,128 (1), 628-635)
The TMB-5 of road various concentrations at different temperatures induces the crystallization behavior of PP.Wide-angle x-ray scattering shows：TMB-5 is one
The decisive nucleator of temperature.
Documents (Journal of Applied Polymer Science, 2011,119 (3):1374-1382、
Macromolecules,2009,42(17),6647-6655、Journal of Applied Polymer Science,2013,
129(5):2663-2670、Journal of Applied Polymer Science,2002,86(3):531-539 and
Polymer,1999,40(5):1219-1222) report and the change of crystallization condition is caused to micro-structural by the addition of TMB-5
Influence, as a result shows, accelerates the formation that cooling velocity is conducive to β-PP, and β-PP proportions and the product for ultimately forming
Mechanical property all depends greatly on the concentration of TMB-5.
Chinese patent (application number 02134498.1) discloses the system of a kind of novel polypropylene beta crystal-type nucleater and its gained
Product.The organic cooperation of rare earth formed containing one or more rare earth element and one or more organic compound in the nucleator
Thing.
Although α-crystal formation is under field conditions (factors) easily to be formed, because its crystalline rate is slow, spherocrystal grain is big, and brilliant
Grain size heterogeneity, therefore in many researchs and practical application, people form α-crystal formation often through addition α nucleators.
Documents (plastics science and technology 2011,39 (2):90-93) report a kind of glucitols (ZC-2 types) nucleator pair
The influence of crystalling propylene, light transmittance and mechanical property, as a result shows, with the increase of ZC-2 type nucleation agent contents, PP's is saturating
Light rate, tensile strength and elastic modelling quantity are all improved, and elongation at break and spherulite size are reduced.
Documents (International Journal of Polymer Analysis and
Characterization 2010,15(7):450-459) compare and add in iPP and be not added with nucleator (DMDBS), as a result
Display：Under same rate of temperature fall, the addition of nucleator can significantly improve the crystallization peak temperature (T of iPPp).Additionally, non-
Under isothermy, nucleator is added to change spherulitic growth pattern.
Documents (Journal of Thermal Analysis and Calorimetry 2002,68 (1):61-
74) DBS, MDBS, DMDBS these three Sorbitol Nucleators are compared to polyacrylic using differential scanning calorimeter (DSC)
Nucleating effect, when three kinds of concentration of nucleator are 0.3%, respectively with their modified PP compared with unmodified PP,
Crystallization temperature has different degrees of raising.
Documents (Journal of Macromolecular Science, Part B:Physics 2003,42(3):
Aryl-heterocyclic phosphate nucleator 467-478) is have studied, and their meltings and crystal property to PP are have studied using DSC
Influence.Experimental result finds that the addition of nucleator changes melting and the crystallization behavior of PP, and the addition of every kind of nucleator is to PP's
Crystallization temperature has different degrees of raising.
Documents (petrochemical industry 2003,32 (9):771-774、Journal of Applied Polymer
Science 2006,101(5):3307-3316 and Journal of Applied Polymer Science 2003,88 (2):
One-step synthesis method 8 kinds of aryl-heterocyclic phosphate (monovalence, divalence, the salt of trivalent metal) class nucleator 297-301) is utilized, and
Nucleating effect to them is compared, it is demonstrated experimentally that the nucleating effect of univalent metal salt is substantially better than other two classes nucleation
Agent.
Documents (Journal of Applied Polymer Science 2006,100 (6):4868-4874) use
2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphate (sodium, lithium, potassium) is used as nucleator, and it is right to have studied them
Influences of the iPP in optics, mechanics and crystallization behavior.Result shows that single metal phosphate has significant nucleation to imitate to iPP
Really, nucleation process almost no any effect of two or three compound of metal phosphate to iPP.
Documents (synthetic resin and plastics 2004,21 (4):46-49) utilize differential scanning calorimeter and polarized light microscopy
Mirror have studied influence of the organic phosphate nucleating agent to the crystallization behavior and mechanical property of PP.Result shows, as addition 0.2wt%
Nucleator when, the tensile strength and bending modulus of PP have different degrees of raising.
Documents (plastics industry 2005,33:The performance for 171-173) reporting organophosphorus ester nucleated polypropylene is ground
Study carefully, organophosphorus compounds nucleator is polyacrylic effective Stiffening agent.Appropriate organophosphorus ester is added in PP can be improved
The dynamic storage modulus of PP, and may be such that the glass transition temperature of PP increases.
Documents (Changsha science and engineering journal 2008,5 (4):86-90) have studied organic phosphates nucleator Irgastab NA-
11 and ADK NA-21 and Sorbitol Nucleator Irgaclear DM and Millad 3988 go to Properties of Polypropylene and crystallization
For influence.Result of study shows that organic phosphates nucleator is better than glucitols nucleation to the raising effect of the mechanical property of PP
Agent, and improvement of the latter in terms of the PP transparencys is significantly better than organic phosphates nucleator.And on enhancing the transparency, glucitols
Better than the Phosphorus nucleator of machine.
Documents (Zhongshan University's journal 2002,41 (1):Be have studied using differential scanning calorimetry (DSC) (DSC) in 43-45)
Phosphoric acid salt nucleator (A) and Sorbitol Nucleator (D) nucleation PP samples Isothermal crystallization behavior and melting property.Result shows
The addition of nucleator, shortens the flexible chain of PP, improves the integrality of PP crystallizations.
Documents (synthetic resin and plastics 1998,15 (2):Substituted aromatic heterocyclic phosphate (A) is compared in 62-66)
With glucitols (respectively B, C, D, E, F) influence of the nucleator to PP crystallization behaviors and mechanical property.Result shows, adds phosphorus
The rigidity that the PP of hydrochlorate nucleator has had, can cause that the tensile strength and bending modulus of PP improve 10% and 30% respectively.
Documents (plastics science and technology 2014,42 (4):Organophosphorus ester and its derivative are have studied in 120-124) to poly-
The influence of propylene performance.Result finds, when the content of nucleator is 0.2%, organophosphorus ester, sodium salt and aluminium salt respectively can be with
The crystallization temperature and bending modulus of PP is caused to be improved.
Documents (Polymer Engineering＆Science 2015,55 (1):22-28) have studied 2,2 '-methylene
Base-bis- (4,6- di-tert-butyl-phenyls) sodium phosphate (NA-11) 2,2 '-methylene-bis- (4,6- di-tert-butyl-phenyls) ammonium phosphate
(An) to the influence of iPP nucleation performances, properties test result shows that An and NA-11 has same nucleation energy to polypropylene
Power.
The melt temperature of organic phosphate is generally higher, bad dispersibility, only transparent come modified PP with organic phosphate
Property is not so good.Organic phosphate and other additive compounds are maximized enhancing organic phosphate by ordinary circumstance, many scientific research persons
Nucleation performance in PP.
Documents (composite journal 2016,33 (9):Reported in 2006-2012) 2,2 '-methylene-bis--(4,
6- di-tert-butyl-phenyls) sodium phosphate (NA-11) and bicyclic two kinds of nucleators of [2,2,1]-heptane -2,3- Sodium Dicarboxylic Acids (NA-CA)
Compounded, studied them to isotactic polypropylene (iPP) mechanical property, the influence of crystallization behavior.Research shows, this to be re-dubbed
Core agent has cooperative effect in terms of polyacrylic mechanical property and crystallization behavior is improved.
Documents (Journal of Applied Polymer Science 2012,123 (1):617-626) by two
2,2 '-methylene of α nucleators-bis- (4,6- di-tert-butyl-phenyls) sodium phosphates (NA11) and nanoclay (NC) are planted according to certain
Ratio forms compounding nucleator and is added in iPP, and compounding nucleator is studied using WAXD, POM, SEM and DSC to iPP mechanics
The influence of performance and crystallization behavior.Result shows that the crystal form and spherocrystal rate of rise of iPP are subject to being total to for both NA11 and NC
With influence.
Documents (plastics 2010,39 (1):48-50) using petrographic microscope (PLM), photoelectricity mist degree instrument, differential thermal analysis
And Mechanics Performance Testing has investigated organic phosphate (NA-21) and Ludox and compounded nucleator to the iPP transparencys, crystallization (DSC)
Behavior and the influence of mechanical property.Test result indicate that：NA-21 has the good heterogeneous nucleating effect that cooperates with Ludox, compounding
Nucleator also has significant effect to improving the impact strength of iPP and drawing high intensity.
Documents (synthetic resin and plastics 2006,23 (5):14-16) report the organic phosphoric acid with disc structure
Salt nucleator HBP can significantly improve the crystallization behavior and combination property of PP.When the HBP of 0.2wt% is added, the crystallinity of PP
52.2% is brought up to from 46.4%, bending strength and bending modulus have been respectively increased 23% and 21%, heat distortion temperature and crystallization
Temperature is respectively increased 23.9 DEG C and 22.7 DEG C, and the mist degree of product then reduces 60%.
Documents (Journal of Polymer Science:Part B:Polymer Physics 2010,48:
653-665, petrochemical industry 2011,40 (6):608-613) by a kind of alpha-crystal form nucleator and a kind of beta crystal-type nucleater with certain
Compositely proportional regulates and controls polyacrylic rigidity and toughness, and the polypropylene material that rigidity and toughness are improved simultaneously is obtained with this.
It is also a kind of effectively to improve its mechanical performance and heat is steady to inorganic nanoparticles filler is added in acrylic resin
The method of qualitative energy.
Chinese patent (application number 201010609131.1) discloses a kind of mica modified polypropylene composite material, and with
The increase of mica filled amount, the bending modulus and hardness of polypropylene material have different degrees of raising.
Chinese patent (application number CN201110407243.3) discloses a kind of high intensity, superhigh tenacity polypropylene nano and answers
Condensation material and preparation method thereof, the nanometer composite polypropylene material is made up of following raw material according to percentage by weight：Polypropylene
40-97%, nano-sized filler 1-15%, common micro-scaled filler 1-25%, compatilizer 0-3%, elastic body toughening agent 1-25%, stabilization
Agent 0.1-2%, other additives 0-5%.
Chinese patent (application number CN201110198285.0) discloses a kind of rigidity-toughness balanced polypropylene, by the following raw material according to
Weight is than composition：Polypropylene 45%-90%, coupling agent modified low mesh number talcum powder 5%-20%, high mesh number talcum powder 5%-
30%th, toughener 0%-15%, antioxidant 0%-2% and other additives 0%-2%；By the base being formulated in tenacity-increased profax
Added on plinth it is a kind of can effectively make up the rigid inorganic filler that toughness reinforcing is sacrificed so that be obtained rigidity-toughness balanced polypropylene
Composite.
Chinese patent (application number CN200810203127.8) discloses a kind of polypropylene composite materials with rigid-tough balance
Material and preparation method thereof, is prepared according to the raw material of following weight %：Polypropylene 55-95%, wollastonite 3-30%, other
Inorganic filler 0-10%, toughener POEO-20%, antioxidant 0.1-2%, other auxiliary agents 0-5.0%, the method is by toughness reinforcing
Added on the basis of PP composite material it is a kind of can effectively make up the rigid inorganic filler that its toughness reinforcing is sacrificed so that
To the product of rigidity-toughness balanced.
It is also a kind of method for effectively improving its mechanical performance and thermal stability to fiber is added in acrylic resin.
Fiber includes：Glass fibre, natural fiber and synthetic fibers.Compared to other fibers, glass fiber reinforced polypropylene has good
Comprehensive mechanical property and heat endurance.And in glass fiber reinforced polypropylene material, one common issue is that fiber and poly-
The weak interface interaction of propylene, generally improves interface interaction power between them by adding bulking agent.Additionally, maleic anhydride grafting
Polypropylene be a kind of one of most common bulking agent, the maleic anhydride of polarity can be played between glass fibre and polypropylene
Very strong adhesive attraction.
In fiberglass surfacing grafting polymer molecular chain be a kind of improvement fiber and interlaminar resin boundary strength very
Effective method.These backbones for being grafted on fiberglass surfacing preferably can be penetrated with matrix resin molecule and
The effect of tangling, so as to improve interface binding intensity (the Macromolecular Rapid Communications of fiber and resin
2011,32(12):859-869), so improve fiber glass thermoplastics mechanical property.Meanwhile, this grafting side
Method can greatly expand the species of fiberglass surfacing functional group, so as to expand the choosing of the matrix macromolecule resin of composite
With scope, it is also possible to realize freely adjusting to composite material interface adhesion strength size by controlling the length of grafting molecules chain
Control.
Isocyanates is the active electrophilic reagent of a class, quickly can be reacted with hydroxyl and amino etc..Isocyanates
Have been shown to be chemically reacted with the hydroxyl of fiberglass surfacing, make such that it is able to the coupling agent as glass fibre
With.Documents (Chemical Communcations2002,1846-1847) are reported to be done using the isocyanic acid butane of 1,4- bis-
It is coupling agent, zeolite granular is loaded on glass fibre.Documents (Journal of Biomaterials
Applications 2013,28(3):354-366) report and use hexamethylene diisocyanate (HDI) as glass fibre
Modified coupling agent.
Documents (RSC Advances 2015,5l:4066-40677；Current Organic Chemistry
2015,19(11):991-1010；Engineering plastics application 2015,43 (4):A kind of glass fibre multistep 103-108) is reported to change
The method of property, the amine or alcohols of glass fibre priority amino silicone, diisocyanate and Long carbon chain are entered to fiber
Row impregnation process.Compare with other surface grafting means, the method for this multistep graft modification uses relatively inexpensive siloxanes
And isocyanates, organic long-chain can be grafted on fiberglass surfacing under mild conditions.Compared to untreated or silica
The glass fibre of alkane treatment, the glass fiber reinforced thermoplastics composite that the glass fibre being grafted with the method is produced has more
Good tensile property, and interface binding intensity higher.
Documents (Materials 2012,5:1084-1113) report and repaiied with MAO and 9- decen-1-ols
Glass fiber reinforced polypropylene after decorations, as a result shows：Compared with unmodified glass fiber reinforced polypropylene material, after modification
Glass fiber reinforced polypropylene material intensity and toughness all improve three times, meanwhile, glass fibre is made with polyacrylic interface
Firmly improve twice.
Documents (Composites:Part A 1996,27A:Fibre length and concentration 477-484) be have studied to glass
The influence of glass TRPP material property.
Chinese patent (application number 201210075453.1) discloses a kind of Fiberglass-reinforcepolypropylene polypropylene plastic, it be by
Following component (calculating by weight) compositions：100 parts of polypropylene, glass fibre 20-40 parts, barium sulfate 10-20 parts, PP-g-
MAH10-15 parts, 0.2-0.4 parts of HK-550 surfactants, melamine cyanurate 10-20 parts, antioxidant 1010 0.1-0.3
Part.Above-mentioned gained PP composite material, with high rigidity, lower shrinkage, high mechanical properties, heat-resist etc..
Chinese patent (application number 201410199700.8) discloses a kind of Fiberglass-reinforcepolypropylene polypropylene plastic and its system
Preparation Method, its composition is (by weight)：40-60 parts of PP resin, 25-35 parts of glass fibre, 15-25 parts of PP-g-MAH is compatible
Agent, 0.1-0.5 parts of antioxidant.Material prepared by the invention has rigidity high, can be applicable to household electrical appliance, plastic pipe,
In the products such as automobile test specimen.
In theory, two methods of nucleater modified and fiber reinforcement are combined, synthesizing new PP composite material,
The high-strength, Gao Mo of energy, the PP composite material of toughness reinforcing are further developed, researcher has carried out some trials.
Documents (plastics industry 2016,44 (4):Rare earth nucleating agent/glass fibre is reported in 106-110) to be modified
The preparation of PP composite material and its performance study, they are prepared by the raw material of following quality %：Polypropylene 88.75~
68.95%；Glass fibre 30%；Rare earth nucleating agent 0.05-0.25%；Antioxidant 1%.
Documents (Journal of Thermal Analysis and Calorimetry 2013,114:229-
237) nano-calcium carbonate and polyethylene terephthalate (PET) fiber for being loaded with carboxylic acids nucleating agent is reported in
Common modified polypropene, they will be loaded with the components such as the nano-calcium carbonate of carboxylic acids nucleator, PET and match somebody with somebody according to certain
Than being added to extrusion, granulation in double screw extruder after well mixed, finally with injection machine by above-mentioned gained particle injection moulding.
Documents (Composites Science and Technology 2014,96:Reported in 56-62) and passed through
It is to addition nucleating agent in long glass fiber reinforced polypropylene material and further further to material with this method of annealing
The method for processing to prepare PP composite material, is put into twin-screw and squeezes after the components such as nucleating agent, polypropylene are well mixed
Go out in machine, long glass fibres is added in twin-screw by side feeding machine, therewith, extrusion, granulation obtains what nucleating agent was modified
Glass fiber reinforced polypropylene.
Chinese patent (application number CN201310293883.5) discloses a kind of preparation method of PP composite material, its
Formula fraction meter by weight, including 60-70 parts of polypropylene, 25-27 parts of glass fibre, 2-4 parts of compatilizer, 2-4 parts
Toughener, 0.2-0.4 parts of antioxidant, 0.2-0.5 parts of lubricant and 0.2-0.4 parts of nucleator.By above-mentioned component according to
Proportioning is extruded during double screw extruder is added to after being well mixed, granulation obtains intended particle.
However, the effect that two methods of nucleater modified and fiber reinforcement are cooperateed with could not be reached using above-mentioned several method,
Because directly being extruded after nucleating agent and glass fibre directly mixing, being granulated, because glass fibre is used as one kind
The introducing of exogenous impurity so that nucleator can not play the effect of its regulation and control crystalling propylene behavior, draws so as to result in material
Stretch the reduction of intensity.
In sum, to aim to provide this one kind with low cost, simple and easy to apply for invention, and nucleator is regulated and controled into crystallization behavior and fibre
The preparation method of the PP composite material that dimension enhancing is combined.In order to solve in above-mentioned several method directly by polypropylene with into
Core agent and fiber are mixed, because glass fibre is used as a kind of introducing of exogenous impurity so that nucleator can not play its tune
The problem of the effect of crystalling propylene behavior is controlled, the present invention uses two-step method first, regulate and control polyacrylic using nucleator first
Crystallization behavior, is then combined with glass fibre again, and nucleator regulation and control and fiber reinforcement are effectively combined, and collaboration is improved
The combination property of PP composite material.Meanwhile, the base glass fiber that the inventive method is used is cheap and easy to get, is used
The process is simple of twin-screw extrusion, is easy to implement large-scale production and applies.
The content of the invention
Present invention aim at, there is provided a kind of low cost, process is simple, nucleator regulation and control and fiber reinforcement are effectively tied
Altogether, collaboration improve PP composite material combination property PP composite material preparation method, the method be by
Polypropylene, bulking agent, glass fibre, nucleator, antioxidant are made of two-step method, first, first induce polypropylene with nucleator
Generation crystal transfer, is then combined the method that is further enhanced therewith with glass fibre again, solves straight in conventional method
Connect and mixed polypropylene with nucleator and fiber, because glass fibre is used as a kind of introducing of exogenous impurity so that nucleation
Agent can not effectively play the problem of the effect of its regulation and control crystalling propylene behavior.The present invention increases nucleator regulation and control and glass fibre
Effectively combine by force, collaboration improves the combination property of PP composite material, poly- third obtained by the method for the invention
Not only comprehensive mechanical property is good for alkene composite, and heat endurance is high.Meanwhile, the base glass fiber for being used is cheap and easy to get,
The process is simple of the twin-screw extrusion for being used, low cost is easy to implement large-scale production and applies.
A kind of preparation method of PP composite material of the present invention, follow these steps to carry out：
By mass fraction respectively by polypropylene 69.3-79.6%, nucleator 0.1-0.3%, antioxidant 0.2% in temperature 80
12h is placed in DEG C baking oven, is then placed in mixing in high-speed mixer, be added in double screw extruder and extrude, granulation, wherein double
Screw Parameters are：One area's temperature is 160 ± 10 DEG C, and two area's temperature are 180 ± 10 DEG C, and three area's temperature are 210 ± 10 DEG C, four area's temperature
It is 220 ± 10 DEG C to spend, and five area's temperature are 220 ± 10 DEG C, and head temperature is 210 ± 10 DEG C, and twin-screw rotating speed is 70-80r/min,
Feeding machine rotating speed is 4-8r/min, and pelleter rotating speed is 200-400r/min, and wherein nucleator is N, N '-dicyclohexyl -2,6-
Aphthalimide, N, N '-dicyclohexyl terephthalamide, 2,2 '-methylene-bis- (4,6- di-tert-butyl-phenyls) sodium phosphates,
[double 2,2 '-methylene-(4,6- di-t-butyls phenoxy group) phosphoric acid] hydroxy Al, two (benzal of 3,4- dimethyl two) sorbierites or 1,
3:2,4- MDBSs；Antioxidant is by four propionates and three (2,4- di-tert-butyl-phenyls) phosphorous
Acid esters is 1 in mass ratio:1 compounding is formed；
B, will be granulated in step a and overnight dried in temperature 60 C baking oven, glass fibre 20-30% and increase-volume with drying
Extruded in double screw extruder after agent 0.1-0.2% is well mixed, granulation, wherein twin-screw parameter is：One area's temperature is 160
± 10 DEG C, two area's temperature are 180 ± 10 DEG C, and three area's temperature are 210 ± 10 DEG C, and four area's temperature are 220 ± 10 DEG C, and five area's temperature are
220 ± 10 DEG C, head temperature is 210 ± 10 DEG C, and twin-screw rotating speed is 70-80r/min, and feeding machine rotating speed is 4-8r/min, is cut
Grain machine rotating speed is 200-400r/min；Glass fibre is alkali-free chopped strand glass fibers；Bulking agent is that grafting rate is quality point
The maleic anhydride inoculated polypropylene of number 0.8-1.0%；
C, the granulation in step b is hot-forming through hot press, pressurize temperature is 220 DEG C, and dwell pressure is 40MPa, most
Afterwards by cooling down water cooling, PP composite material is obtained.
A kind of preparation method of PP composite material of the present invention, in the method nucleator be nucleating agent or α-
Nucleator, its structural formula is：
N, N '-dicyclohexyl -2,6- aphthalimides
N, N '-dicyclohexyl terephthalamide
2,2 '-methylene-bis- (4,6- di-tert-butyl-phenyls) sodium phosphate
[double 2,2 '-methylene-(4,6- di-t-butyls phenoxy group) phosphoric acid] hydroxy Al
Two (benzal of 3,4- dimethyl two) sorbierites
1,3:2,4- MDBSs
A kind of preparation method of PP composite material of the present invention, the method has every mechanical property higher
Can, while possessing heat endurance very high, excellent combination property；By using nucleater modified polypropylene, can obtain respectively
Rigidity, toughness polypropylene material very high；Afterwards, in order that obtain prepared material possesses good intensity simultaneously, to matrix
In introduce alkali-free glass fibre, its addition will improve polypropylene material strength and stiffness；Meanwhile, in order to improve glass
Interface interaction power between fiber and polypropylene matrix, adds the polypropylene of polar micromolecules maleic anhydride modification as increase-volume
Agent improves the interface interaction power between glass fibre and matrix；By methods described, PP composite material is not only caused
Intensity, rigidity, heat distortion temperature are significantly improved, and the performance such as elongation percentage and notch impact strength is also greatly enhanced.
A kind of preparation method of PP composite material of the present invention, its advantage is such as compared with prior art for the method
Under：
(1) present invention uses two-step method, first induces polypropylene that crystal transfer, Ran Houzai occur with β or α-nucleator first
The method that is further enhanced is combined therewith with glass fibre, is solved in conventional method directly by polypropylene and nucleating agent
And fiber is mixed, because glass fibre is used as a kind of introducing of exogenous impurity so that β or α-nucleator can not be played effectively
The problem of the effect of its regulation and control crystalling propylene behavior.
(2) the inventive method raw material is cheap and easy to get, and process is simple, reaction condition is easily achieved.
(3) present invention have selected β or α-nucleator not only nucleation efficiencies be high, and stability and good in the dissolubility of matrix.
(4) glass fibre used in the present invention, not only excellent in mechanical performance, and cost is relatively low.
(5) raw material used in the present invention is technical grade, and this is cheap on cost relative to many preparation methods.
(6) the product heat endurance obtained by the present invention is good, excellent in cushion effect, therefore, it is possible to stable application in harsh ring
Border is such as：High temperature, strong acid, highly basic and organic solvent.
Brief description of the drawings
Fig. 1 is the XRD of the composite prepared by the embodiment of the present invention 1；
Fig. 2 is the DSC figures of the composite prepared by the embodiment of the present invention 1.
Specific embodiment
Embodiment 1
A, mass fraction weigh polypropylene 79.3%, antioxidant 0.2%, nucleating agent N, N '-dicyclohexyl -2,6- naphthalenes two
Formamide 0.3%, 12h is dried in 80 DEG C of baking ovens of temperature, is then placed in mixing in high-speed mixer, is then added to twin-screw and is squeezed
Go out in machine and extrude, granulate, wherein twin-screw parameter is：One area's temperature is 160 DEG C, and two area's temperature are 180 DEG C, and three area's temperature are
210 DEG C, four area's temperature are 220 DEG C, and five area's temperature are 220 DEG C, and head temperature is 210 DEG C, and twin-screw rotating speed is 70r/min, is fed
Material machine rotating speed is 4r/min, and pelleter rotating speed is 200r/min, and wherein antioxidant is by four propionates and three (2,4- bis-
Tert-butyl-phenyl) phosphite ester in mass ratio be 1:1 compounding is formed；
B, will be granulated in step a and overnight dried in temperature 60 C baking oven, glass fibre 20% and bulking agent with drying
0.2% it is well mixed after extruded in double screw extruder, granulation, wherein twin-screw parameter is：One area's temperature is 160 DEG C, two
Area's temperature is 180 DEG C, and three area's temperature are 210 DEG C, and four area's temperature are 220 DEG C, and five area's temperature are 220 DEG C, and head temperature is 210
DEG C, twin-screw rotating speed is 70r/min, and feeding machine rotating speed is 4r/min, and pelleter rotating speed is 200r/min, and wherein glass fibre is
Alkali-free chopped strand glass fibers；Bulking agent is that grafting rate is the maleic anhydride inoculated polypropylene of mass fraction 0.8%；
C, the granulation in step b is hot-forming through hot press, pressurize temperature is 220 DEG C, and dwell pressure is 40MPa, most
Afterwards by cooling down water cooling, PP composite material is obtained.
Properties test result：
Characterize：X-ray diffraction (XRD) sign and differential scanning amount are carried out to implementing the PP composite material obtained by 1
The sign of hot (DSC)：β-crystalline substance is formd by what the XRD of Fig. 1 can be seen that this Success in Experiment, in spite of the doping of glass fibre
(glass fibre can not form β-crystalline substance), the present invention, afterwards with glass fiber reinforcement, is successfully prepared by first being crystallized with nucleator
The PP composite material of β high-crystalline substance content.Seen by the sign of Fig. 2 DSC and can be seen that：PP composite material rises in melting
Occur in that the melting characteristic peak of α-crystalline substance and β-crystalline substance during temperature, and β-crystalline substance melting peak content higher than α-crystalline substance, this and XRD institute
β-the crystalline substance for having high content in the composite of explanation is highly consistent.
Embodiment 2
A, polypropylene 69.3% is weighed by mass fraction, antioxidant 0.2%, (N, N '-dicyclohexyl are to benzene two for nucleating agent
Formamide) 0.3%, it is put into 80 DEG C of baking ovens and dries 12h, it is put into high-speed mixer and mixes, placed in 80 DEG C of baking ovens of temperature
Mix after 12h, be added to extrusion in double screw extruder, granulation, wherein twin-screw parameter is：One area's temperature is 165 DEG C, 2nd area
Temperature is 185 DEG C, and three area's temperature are 215 DEG C, and four area's temperature are 225 DEG C, and five area's temperature are 225 DEG C, and head temperature is 215 DEG C,
Twin-screw rotating speed is 60r/min, and feeding machine rotating speed is 8r/min, and pelleter rotating speed is 300r/min, and wherein antioxidant is by 4 third
Sour pentaerythritol ester and three (2,4- di-tert-butyl-phenyls) phosphite esters are 1 in mass ratio:1 compounding is formed；
B, will be granulated in step a and overnight dried in temperature 60 C baking oven, glass fibre 30% and bulking agent with drying
0.2% it is well mixed after extruded in double screw extruder, granulation, wherein twin-screw parameter is：One area's temperature is 165 DEG C, two
Area's temperature is 185 DEG C, and three area's temperature are 215 DEG C, and four area's temperature are 225 DEG C, and five area's temperature are 225 DEG C, and head temperature is 215
DEG C, twin-screw rotating speed is 60r/min, and feeding machine rotating speed is 8r/min, and pelleter rotating speed is 300r/min, and wherein glass fibre is
Alkali-free chopped strand glass fibers；Bulking agent is that grafting rate is the maleic anhydride inoculated polypropylene of mass fraction 0.8%；
C, the granulation in step b is hot-forming through hot press, pressurize temperature is 220 DEG C, and dwell pressure is 40MPa, most
Afterwards by cooling down water cooling, PP composite material is obtained.
Embodiment 3
A, polypropylene 75% is weighed by mass fraction, antioxidant 0.2%, α-nucleator 2,2 '-methylene-bis- (4,6- bis-
Tert-butyl-phenyl) sodium phosphate 0.2%, after placing 12h in 80 DEG C of baking ovens of temperature, mixing in high-speed mixer is put into, add
Extruded in double screw extruder, granulation, wherein twin-screw parameter is：One area's temperature is 150 DEG C, and two area's temperature are 170 DEG C, three
Area's temperature is 200 DEG C, and four area's temperature are 210 DEG C, and five area's temperature are 210 DEG C, and head temperature is 200 DEG C, and twin-screw rotating speed is
80r/min, feeding machine rotating speed is 5r/min, and pelleter rotating speed is 350r/min, wherein, antioxidant is by four propionates
In mass ratio it is 1 with three (2,4- di-tert-butyl-phenyls) phosphite esters:1 compounding is formed；
B, will be granulated in step a and overnight dried in temperature 60 C baking oven, glass fibre 24.5% and increase-volume with drying
Extruded in double screw extruder after agent 0.1% is well mixed, granulation, wherein twin-screw parameter is：One area's temperature is 150 DEG C,
Two area's temperature are 170 DEG C, and three area's temperature are 200 DEG C, and four area's temperature are 210 DEG C, and five area's temperature are 210 DEG C, and head temperature is 200
DEG C, twin-screw rotating speed is 80r/min, and feeding machine rotating speed is 5r/min, and pelleter rotating speed is 350r/min, and wherein glass fibre is
Alkali-free chopped strand glass fibers；Bulking agent is that grafting rate is the maleic anhydride inoculated polypropylene of mass fraction 0.9%；
C, the granulation in step b is hot-forming through hot press, pressurize temperature is 220 DEG C, and dwell pressure is 40MPa, most
Afterwards by cooling down water cooling, PP composite material is obtained.
Embodiment 4
A, polypropylene 78% is weighed by mass fraction, antioxidant 0.2%, α-nucleator [double 2,2 '-methylene-(4,6- bis-
Tert-butyl benzene epoxide) phosphoric acid] hydroxy Al 0.3%, 12h is placed in 80 DEG C of baking ovens of temperature, mixing in high-speed mixer is put into, then
Extrusion in double screw extruder, granulation are added to, wherein twin-screw parameter is：One area's temperature is 170 DEG C, and two area's temperature are 190
DEG C, three area's temperature are 220 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 230 DEG C, and head temperature is 220 DEG C, twin-screw rotating speed
It is 75r/min, feeding machine rotating speed is 6r/min, and pelleter rotating speed is 400r/min, wherein, antioxidant is by four propionic acid pentaerythrites
Ester and three (2,4- di-tert-butyl-phenyls) phosphite esters are 1 in mass ratio:1 compounding is formed；
B, will be granulated in step a and overnight dried in temperature 60 C baking oven, glass fibre 21.3% and increase-volume with drying
Extruded in double screw extruder after agent 0.2% is well mixed, granulation, wherein twin-screw parameter is：One area's temperature is 170 DEG C,
Two area's temperature are 190 DEG C, and three area's temperature are 220 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 230 DEG C, and head temperature is 220
DEG C, twin-screw rotating speed is 75r/min, and feeding machine rotating speed is 6r/min, and pelleter rotating speed is 400r/min, and wherein glass fibre is
Alkali-free chopped strand glass fibers；Bulking agent is that grafting rate is the maleic anhydride inoculated polypropylene of mass fraction 0.9%；
C, the granulation in step b is hot-forming through hot press, pressurize temperature is 220 DEG C, and dwell pressure is 40MPa, most
Afterwards by cooling down water cooling, PP composite material is obtained.
Embodiment 5
A, polypropylene 72% is weighed by mass fraction, antioxidant 0.1%, α-nucleator two (benzal of 3,4- dimethyl two) mountain
Pears alcohol 0.1%, 12h is placed in 80 DEG C of baking ovens of temperature, is put into mixing in high-speed mixer, is then added in double screw extruder
Extrusion, granulates, and wherein twin-screw parameter is：One area's temperature is 155 DEG C, and two area's temperature are 175 DEG C, and three area's temperature are 205 DEG C, four
Area's temperature is 215 DEG C, and five area's temperature are 215 DEG C, and head temperature is 205 DEG C, and twin-screw rotating speed is 78r/min, feeding machine rotating speed
It is 7r/min, pelleter rotating speed is 250r/min, and wherein antioxidant is by four propionates and three (2,4- di-tert-butyls
Base) phosphite ester in mass ratio be 1:1 compounding is formed；
B, will be granulated in step a and overnight dried in temperature 60 C baking oven, glass fibre 27.7% and increase-volume with drying
Extruded in double screw extruder after agent 0.1% is well mixed, granulation, wherein twin-screw parameter is：One area's temperature is 155 DEG C,
Two area's temperature are 175 DEG C, and three area's temperature are 205 DEG C, and four area's temperature are 215 DEG C, and five area's temperature are 215 DEG C, and head temperature is 205
DEG C, twin-screw rotating speed is 78r/min, and feeding machine rotating speed is 7r/min, and pelleter rotating speed is 250r/min, and wherein glass fibre is
Alkali-free chopped strand glass fibers；Bulking agent is that grafting rate is the maleic anhydride inoculated polypropylene of mass fraction 1.0%；
C, the granulation in step b is hot-forming through hot press, pressurize temperature is 220 DEG C, and dwell pressure is 40MPa, most
Afterwards by cooling down water cooling, PP composite material is obtained.
Embodiment 6
A, polypropylene 76% is weighed by mass fraction, antioxidant 0.2%, α-nucleator 1,3:2,4- bis- (to methyl benzal)
Sorbierite 0.15%, 12h is placed in 80 DEG C of baking ovens of temperature, is put into mixing in high-speed mixer, is then added to twin-screw extrusion
Extruded in machine, granulation, wherein twin-screw parameter is：One area's temperature is 160 DEG C, and two area's temperature are 175 DEG C, and three area's temperature are 215
DEG C, four area's temperature are 210 DEG C, and five area's temperature are 215 DEG C, and head temperature is 205 DEG C, and twin-screw rotating speed is 80r/min, feeding machine
Rotating speed is 8r/min, and pelleter rotating speed is 400r/min, wherein, antioxidant is by four propionates and three (2,4- bis- uncles
Butyl phenyl) phosphite ester in mass ratio be 1:1 compounding is formed；
B, will be granulated in step a and overnight dried in temperature 60 C baking oven, glass fibre 23.55% and increase-volume with drying
Extruded in double screw extruder after agent 0.1% is well mixed, granulation, wherein twin-screw parameter is：One area's temperature is 160 DEG C,
Two area's temperature are 175 DEG C, and three area's temperature are 215 DEG C, and four area's temperature are 210 DEG C, and five area's temperature are 215 DEG C, and head temperature is 205
DEG C, twin-screw rotating speed is 80r/min, and feeding machine rotating speed is 8r/min, and pelleter rotating speed is 400r/min, and wherein glass fibre is
Alkali-free chopped strand glass fibers；Bulking agent is that grafting rate is the maleic anhydride inoculated polypropylene of mass fraction 1.0%；
C, the granulation in step b is hot-forming through hot press, pressurize temperature is 220 DEG C, and dwell pressure is 40MPa, most
Afterwards by cooling down water cooling, PP composite material is obtained.
Claims (1)
1. a kind of preparation method of PP composite material, it is characterised in that follow these steps to carry out：
A, by mass fraction respectively by polypropylene 69.3-79.6%, nucleator 0.1-0.3%, antioxidant 0.2% in the baking of 80 DEG C of temperature
12 h are placed in case, is then placed in mixing in high-speed mixer, be added to extrusion in double screw extruder, granulation, wherein double spiral shells
Bar parameter is：One area's temperature is 160 ± 10 DEG C, and two area's temperature are 180 ± 10 DEG C, and three area's temperature are 210 ± 10 DEG C, four area's temperature
It is 220 ± 10 DEG C, five area's temperature are 220 ± 10 DEG C, head temperature is 210 ± 10 DEG C, twin-screw rotating speed is 70-80 r/min,
Feeding machine rotating speed is 4-8 r/min, and pelleter rotating speed is 200-400r/min, and wherein nucleator is N, N '-dicyclohexyl -2,6-
Aphthalimide, N, N '-dicyclohexyl terephthalamide, 2,2 '-methylene-bis-（4,6- di-tert-butyl-phenyls）Sodium phosphate,
[double 2,2 '-methylene-（4,6- di-t-butyl phenoxy groups）Phosphoric acid] hydroxy Al, two（The benzal of 3,4- dimethyl two）Sorbierite or 1,
3:2,4- MDBSs；Antioxidant is by four propionates and three（2,4- di-tert-butyl-phenyls）Phosphorous
Acid esters is 1 in mass ratio:1 compounding is formed；
B, will be granulated in step a and overnight dried in temperature 60 C baking oven, glass fibre 20-30% and bulking agent with drying
Extruded in double screw extruder after 0.1-0.2% is well mixed, granulation, wherein twin-screw parameter is：One area's temperature be 160 ±
10 DEG C, two area's temperature are 180 ± 10 DEG C, and three area's temperature are 210 ± 10 DEG C, and four area's temperature are 220 ± 10 DEG C, and five area's temperature are
220 ± 10 DEG C, head temperature is 210 ± 10 DEG C, and twin-screw rotating speed is 70-80 r/min, and feeding machine rotating speed is 4-8 r/min,
Pelleter rotating speed is 200-400 r/min；Glass fibre is alkali-free chopped strand glass fibers；Bulking agent is that grafting rate is quality
The maleic anhydride inoculated polypropylene of fraction 0.8-1.0%；
C, the granulation in step b is hot-forming through hot press, pressurize temperature is 220 DEG C, and dwell pressure is 40 MPa, is finally led to
Supercooled water is cooled down, and obtains PP composite material.
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| CN108329590A (en) * | 2018-02-08 | 2018-07-27 | 贵州省材料产业技术研究院 | A kind of bimodal crystalline polypropylene composite material and preparation method |
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