CN107513217B

CN107513217B - A kind of polypropylene-base polymer gradient functional material and preparation method thereof

Info

Publication number: CN107513217B
Application number: CN201710773143.XA
Authority: CN
Inventors: 聂敏; 石绍宏; 杨昌华; 王琪
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2017-08-31
Filing date: 2017-08-31
Publication date: 2019-11-22
Anticipated expiration: 2037-08-31
Also published as: CN107513217A

Abstract

The present invention provides a kind of polypropylene-base polymer gradient functional material and preparation method thereof, the material is spread in a certain direction under polypropylene-base material molten condition by α or beta crystal-type nucleater, forms a kind of function-graded material that α or β type crystal is in concentration gradient distribution in the direction in the molding of polypropylene-base material；Preparation method is that have the high molecular polymer carrier of nucleating agent by first preparing polypropylene base and load, and then by the two, in the case where outer surface is bonded prepared by compression molding.The function-graded material has α or β type crystal function-graded material characteristic of structure concentration distribution in gradient in polypropylene base, and without sharp interface, preparation method simple process, and product gradient-structure controlled properties in production process are suitable for promoting.

Description

A kind of polypropylene-base polymer gradient functional material and preparation method thereof

Technical field

The invention belongs to high molecular material and its processing technique field, in particular to a kind of polypropylene-base polymer gradient function Energy material and preparation method thereof.

Background technique

Function-graded material refer in the structure or material of material certain constituent concentration along certain dimension or multiple dimensions by The material of the heterogeneous distribution of certain rule.This gradient-structure can be under the premise of guaranteeing material overall performance, along certain of material Different property or function is presented in dimension or multiple dimensions, finally meets various demands.Currently, developed gradient material The preparation method of material mainly has: chemical vapour deposition technique, physical evaporation method, plasma spraying method, particle gradient ranking method, liquid film Directly the method for forming is infiltrated at method and film.But there are still certain defect, such as manufacturing procedure are multiple for above-mentioned these methods enumerated Miscellaneous, material preparation cost is expensive, and production efficiency is limited, the Gradient Materials thinner thickness produced.

Polypropylene is as the general-purpose plastics in high molecular material, although annual output is more than 10,000,000 tons, to its performance Optimization still has been a concern.Polypropylene has a variety of crystal habits, including α, β, γ and quasi- six side's state type crystal, without the isomorphous Type has different performance advantages, also there is different defects.Such as common two kinds of crystal forms α is brilliant in actual processing, β is brilliant, wherein α Crystal form is monoclinic crystal, and chondritic has the characteristics that stability is good, intensity is high, but toughness is poor；Beta crystal short texture, has Higher toughness, but intensity is relatively low, belongs to metastable state crystal.In general, when being added without nucleating agent, prepare poly- third What alkene mainly generated is alpha type crystal.And in the industrial production, for the polypropylene for obtaining high tenacity, usually add in process of production Enter beta crystal-type nucleater and be homogenously dispersed throughout in polypropylene matrix, to prepare the polypropylene material of high β type crystalline content.But herein In the process, polypropylene self-strength but can be because being greatly reduced containing high concentration β type crystal.In order to make up this strong of material Degree loss often takes addition reinforcing filler compound with polypropylene matrix progress, but this mode again can be to a certain extent The problem of bringing Product Interface compatibility still cannot improve its intensity well.Therefore, a kind of high-strength and high ductility how is obtained Polypropylene material is always the emphasis of this field research.

Chinese patent application 201610341412.0 discloses a kind of extrusion by melting and prepares gradient-structure polymer material Method comprising following steps: using classification the molding technology path of charging-melting extrusion-, wherein classification charging is Refer to design in feeding section and increase a point of feed opening, major constituent polymer feed from main feed opening, and auxiliary component material is from point adding Material mouth charging, and it is added to auxiliary component material in double screw extruder with incrementss every certain time interval.By this Technique can prepare the function polypropylene material of continuous crystallisation degree variation.But during the preparation process, which is limited to squeeze out Equipment divides the design of feed opening, can only obtain the function-graded material product of axial direction, and radial direction is still equal phase structure Distribution, therefore there is certain limitation using field.It is generally believed that in function-graded material field, radially or thickness side To gradient-structure distribution will assign material richer various properties.

Chinese patent ZL02158523.7 discloses a kind of preparation method of polymer gradient functional material, and this method is root According to made polymer gradient material to component and performance requirement, raw material components are subjected to fraction ingredient by gradient proportion, by squeezing Machine extruding sheet melting charge band out will squeeze out melting charge band and be wound or laminate, is made what the Nomenclature Composition and Structure of Complexes changed in gradient Polymer gradient material.Although functionally gradient material (FGM) prepared by the technical solution of the technical solution compared with 201610341412.0 is not only Gradient distribution is realized in the axial direction, also by winding or laminating, effectively realizes the gradient distribution of radial direction, but lose Regret is the influence for being still limited by fraction ingredient, and obtained gradient-structure can only be distributed in radial directions in discontinuous gradient, Such structure will necessarily bring interface problem between layers, such as material is when being impacted, by winding or laminating Between layers easily occur stress concentrate, cause material to crack first in this interface, thus to the globality of material It can impact.

Summary of the invention

In view of the foregoing defects the prior art has and problem, the purpose of the present invention is to provide a kind of polypropylene-base high scores Sub- function-graded material and preparation method thereof, the function-graded material not only have α or β type crystal in polypropylene base in ladder The function-graded material characteristic of structure concentration distribution is spent, and without sharp interface, preparation method simple process produces in production process Product gradient-structure controlled properties are suitable for promoting.

Polypropylene-base polymer gradient functional material provided by the invention, the material are by α or beta crystal-type nucleater poly- It is spread in a certain direction under propylene based materials molten condition, forms α or β type crystal in the direction when the molding of polypropylene-base material A kind of function-graded material being distributed in concentration gradient.

Normally, the function-graded material includes plate, sheet material, bar, membrane material, tubing and all kinds of profile shapes.It is described Function-graded material is the work being pressed and molded by existing polypropylene-base material in polypropylene-base material molten condition and molding Skill step is realized, described to be diffused as in a certain direction along polypropylene-base material outer surface one side or the multi-lateral to inside polypropylene base Direction diffusion.

The α or beta crystal-type nucleater are dibenzyl sorbitol class nucleating agent, substituted aromatic heterocyclic phosphate class nucleation Any in agent, organic carboxyl acid salt nucleating agent, rare earth compound class beta crystal-type nucleater or aromatic series diamide nucleating agent Kind.

It is further preferred that the dibenzyl sorbitol class nucleating agent is dibenzal sorbitol (DBS), two (to methyl Benzylidene) sorbierite (P-Me-DBS), two (to ethyl benzylidene) sorbierites (P-Et-DBS) or two (3,4- dimethyl benzenes Methylene) sorbierite (DMDBS)；The substituted aromatic heterocyclic phosphate class nucleating agent is to (4- tert-butyl benzene oxygroup) phosphate (NA-10) or bis- (the 2,4- di-t-butyl phenoxy group) phosphate (NA-11) of methyl；The organic carboxyl acid salt nucleating agent is double (p-tert-butyl benzoic acid) hydroxyl aluminium salt (Al-PTBBA) or hexahydro-phthalic acid salt (HHPA)；The rare earth compound class Beta crystal-type nucleater is any beta crystal-type nucleater of WBG series；The aromatic series diamide nucleating agent is any nucleation of TM series Agent.

Through inventor's test of many times, carried out preferably for cost and effect aspect, the nucleating agent is selected as two benzal mountains Pears alcohol (DBS), WBG-II or TMB-5.

The present invention also provides the preparation method of above-mentioned polypropylene-base polymer gradient functional material, processing step is as follows:

(1) polypropylene base is prepared

In the form of polypropylene or polypropylene and auxiliary material mix, melt blending extruding pelletization, then mould according to a conventional method It is molded to obtain polypropylene base,

The polypropylene in the form with auxiliary material mix polyacrylic quality accounting be not less than 60%；

(2) preparation load has the carrier of nucleating agent

Melting temperature is greater than polyacrylic high molecular polymer and α or beta crystal-type nucleater ingredient, is melted according to a conventional method Blending extrusion is granulated, then is pressed and molded to obtain the carrier that load has nucleating agent,

α or beta crystal-type nucleater quality are the 0.1~20% of support material gross mass in the ingredient；

(3) preparation has the polypropylene-base material of gradient-structure

Step (2) resulting vehicle is fitted in the one side or the multi-lateral of the outer surface of polypropylene base obtained by step (1), is carried out Compression molding, it is in concentration gradient structure that carrier is removed after cold pressing to get α the or β type crystal on carrier binding face direction The polypropylene-base material of distribution, as polypropylene-base polymer gradient functional material,

The temperature setting of the compression molding is higher than the melting temperature of polypropylene base, has nucleation agent carrier lower than load The melting temperature of high molecular polymer, clamp time setting are not less than 10s.

Wherein, polypropylene described in step (1) is appointing in homopolypropylene, block copolymerization polypropylene or random polypropylene It is a kind of.

Wherein, auxiliary material described in step (1) include polypropylene filler, reinforcing material, antioxidant, stabilizer, plasticizer, One of colorant is a variety of.Normally, polypropylene selects any one of calcium carbonate, montmorillonite and talcum powder with filler； Polypropylene selects any one of glass fibre, carbon fiber, graphene and cellulose with reinforcing material.

Wherein, melting temperature described in step (2) is greater than polyacrylic high molecular polymer and is nylon, polyester, polysulfones, gathers Any one of carbonic ester or polyphenylene sulfide.

Wherein, in step (2) described ingredient α or beta crystal-type nucleater quality be preferably support material gross mass 1~ 10%.

Wherein, step (2) α or beta crystal-type nucleater are dibenzyl sorbitol class nucleating agent, substituted aryl heterocycle phosphorus Barbiturates nucleating agent, organic carboxyl acid salt nucleating agent, rare earth compound class beta crystal-type nucleater or aromatic series diamide nucleating agent Any one of.

Through inventor's test of many times, preferred for carrying out from the aspect of cost and effect, the nucleating agent is selected as dibenzyl Pitch sorbierite (DBS), WBG-II or TMB-5.

Preferably, at 180 DEG C~240 DEG C, clamp time is controlled in 1min~2h the control of step (3) molding temperature.Molding Time is longer, and nucleating agent diffusion under polypropylene matrix molten condition is bigger, α or β type crystal institute in obtained finished product The concentration gradient structure concentration variation showed is smaller, i.e., in α the or β type crystal concentration along nucleating agent dispersal direction equidistance Numerical value is very poor smaller.It is worth noting that when clamp time controls in a short time (according to polypropylene base and mould type Chamber shape exist variation, can be generally thought is within the scope of 10s~1min), nucleating agent under polypropylene matrix molten condition not Entirety can be diffused to, therefore finished product after molding only partially shows the functional characteristic of gradient-structure.

In step (3), step (2) resulting vehicle is fitted in the one of the outer surface of polypropylene base obtained by step (1) The step of side or more sides are pressed and molded, be according to compression molding institute's converted products have different shape, use demand and Gradient-structure functional requirement is designed, such as when being pressed and molded plate, sheet material, is by polypropylene base and carrier difference mould Be pressed into the form of plate, sheet material, then by carrier be fitted in polypropylene base upper surface lower surface or simultaneously upper and lower surface into Row compression molding, products obtained therefrom can have α or β type crystal along plate, sheet thickness direction in high concentration-low concentration or High concentration-low concentration-high concentration gradient-structure feature；In another example being by polypropylene base mould when being pressed and molded bar It is pressed into the form of bar, carrier is molded into the form of tubing, and dimensional fits are corresponding between tubing and bar, then by the tubing shape The carrier of formula is covered to be pressed and molded in the outer surface of the polypropylene base of rod form, and products obtained therefrom has α or β type crystal edge Polypropylene-base bar outer surface to axis direction is in high concentration-low concentration gradient-structure feature；It is for example managed again in compression molding It is the form that polypropylene base is molded into tubing when material, carrier is molded into the form of bar, and size is matched between tubing and bar It closes and corresponds to, then the polypropylene base of the tubing form is covered and is pressed and molded on the carrier of rod form, products obtained therefrom It is special in high concentration-low concentration gradient-structure along polypropylene-base tubing surface of internal cavity to outer surface direction to have α or β type crystal Sign or carrier are molded into bar and tubing, and the inner core and package respectively as polypropylene-base tubing are managed, according to similar technology scheme Compression molding, it is low in high concentration-along polypropylene-base tubing surface of internal cavity to outer surface direction that products obtained therefrom has α or β type crystal Concentration-high concentration gradient-structure feature.

In order to further illustrate preparing polypropylene-base polymer gradient function plate to compression molding in foregoing description here When, specific process step can are as follows:

(1) polypropylene-base plate is prepared

In the form of polypropylene or polypropylene are with auxiliary material mix, melt blending extruding pelletization, then mould according to a conventional method It is molded to obtain polypropylene-base plate,

(2) preparation load has the carrier plate of nucleating agent

Melting temperature is greater than polyacrylic high molecular polymer and α or beta crystal-type nucleater ingredient, is melted according to a conventional method Blending extrusion is granulated, then is pressed and molded to obtain the carrier plate that the uniform load of thickness has equally distributed nucleating agent,

α or beta crystal-type nucleater quality are 0.1~20%, preferably the 1~10% of support material gross mass in the ingredient；

(3) preparation has the polypropylene-base plate of gradient-structure

Step (2) resulting vehicle plate is placed in polypropylene-base plate upper surface, lower surface or upper following table obtained by step (1) Face, carrier board dimension is not less than polypropylene-base plate and carrier plate is bonded with polypropylene-base plate surface, carries out mould Molded, it is in concentration gradient structure that carrier is removed after cold pressing to get α the or β type crystal on polypropylene-base plate thickness direction The polypropylene-base plate of distribution, as polypropylene-base polymer gradient function plate；

The molding temperature setting of step (3) compression molding is higher than polypropylene fusion temperature, has nucleating agent lower than load Carrier melting temperature, generally 180 DEG C~240 DEG C, clamp time setting be not less than 10s, preferably 1min~2h.

It is noted that the present invention is greater than polyacrylic high molecular polymer as load nucleating agent using melting temperature Carrier, and it is bonded polypropylene matrix compression molding, to reach the technology effect that nucleating agent is diffused in polypropylene fusion state Fruit, using carrier and it is indirect be applied as core agent or other means, be because inventor has found in an experiment, it is negative using carrier Nucleating agent is carried to polypropylene-base material is diffused under molten condition, the degree of nucleating agent diffusion is more uniformly controllable, institute The gradient-structure functional material change of gradient of formation is more uniform, when using beta crystal-type nucleater, α and β type in polypropylene-base body Crystal is interweaved and without sharp interface.When the carrier that load has nucleating agent is the uniform plate of thickness, it is fitted in same Sample is is pressed and molded on the polypropylene-base plate of plate, nucleating agent is along polypropylene-base plate thickness direction diffusion height Unanimously, show that its finished product polypropylene-base plate α or β type crystal concentration at same thickness is more consistent.

In addition, fitting described in step (3) is usually that one side or the multi-lateral of the polypropylene base with carrier in outer surface is bonded It is placed into mold cavity under state, in order to guarantee to be bonded effect, can suitably pressurize to mold cavity；It is removed after the cold pressing Remove carrier, usually removing manually, due to substrate melt processing temperature in carrier melting temperature hereinafter, so carrier and substrate it Between have apparent interface, can directly remove carrier.

In the production of actual industrial metaplasia, polypropylene base and carrier can also add other prior arts in process Other processing aids such as well known colorant, antioxidant, stabilizer, plasticizer, but on condition that, these processing aids will not be to poly- The diffusion of nucleating agent generates adverse effect under propylene substrate molten condition.

It is worth noting that polypropylene-base material during melt molding, itself will form certain density α type crystalline substance Body is pressed and molded for example, by using homopolypropylene (model T30S), and alpha type crystal crystallinity is about 45% after cold pressing；Example again It is such as pressed and molded using random polypropylene (model R200P), alpha type crystal crystallinity is about 20% after cold pressing.Using this hair Bright technical solution, after having used alpha-crystal form nucleating agent, gained finished-product material is alpha type crystal concentration not only structure change in gradient, And alpha type crystal concentration in this kind of material can also be made to be higher than the crystallinity under the conditions of polypropylene natural cooling.

The present invention has the advantage that

1. since the present invention is nucleating agent to be diffuseed to form concentration gradient under thermal drivers, and polypropylene is induced to generate α or β The gradient-structure of type crystal, thus the alpha type crystal that the structure and polypropylene base are formed during melt molding itself is without bright Aobvious interfacial gap, more traditional function-graded material effectively improve the defect of interfacial instability.

2. since the nucleating agent that the present invention adds is diffused by being supported on the intracorporal form of high molecular polymer load In polypropylene base, thus diffusion mode of the nucleating agent under polypropylene fusion state can be made by adjusting support shapes Variation, when carrier be plate when, nucleating agent under thermal drivers often for orientation diffusion form, therefore polypropylene after molding at Product are structure distributions in gradient in a certain direction, and when diffusion length is identical, structure or concentration are more uniform.

3. since preparation method of the present invention not only can be by controlling clamp time, to the thickness of polypropylene base inside gradient structure Degree is controlled, and can also be controlled by being pressed and molded mould therefor type chamber the thickness of material, thus can prepare thickness Controllable function-graded material finished product, or part are the finished product of gradient-structure.

4. preparation method simple process of the present invention, easy to operate, for more traditional preparation process, the method is as a kind of New technology can realize its high-strength and high ductility in certain dimension of material or multiple dimensions, finally meet market to polypropylene material Different demands have the wider scope of application, are suitable for promoting.

5. since method provided by the invention is not required to increase additional equipment in preparation process, thus meeting the big rule of industrialization The requirement of mould production, and applicable system is extensive, and the existing preparation process of effective solution is cumbersome existing for self assembly by coating The problems such as.

Detailed description of the invention

Fig. 1 is that the inside crystal form of the polypropylene-base plate with gradient-structure prepared by the embodiment of the present invention 1 is distributed signal Figure.

Fig. 2 is the petrographic microscope photo of the polypropylene-base plate with gradient-structure prepared by the embodiment of the present invention 1.From It can be observed that being in continuity layer structure in polypropylene beta crystalline substance through-thickness in photo, and with the α crystalline substance of ontology without obvious boundary Face.

Fig. 3 is the X-ray diffractogram of the polypropylene-base plate with gradient-structure prepared by the embodiment of the present invention 1.From figure In can calculate the content (k of polypropylene beta crystalline substance_β) it is that through-thickness is distributed in concentration gradient.

Fig. 4 is that the inside crystal form of the polypropylene-base plate with gradient-structure prepared by the embodiment of the present invention 2 is distributed signal Figure.

Fig. 5 is the petrographic microscope photo of the polypropylene-base plate with gradient-structure prepared by the embodiment of the present invention 2.From It can be observed that being in continuity layer structure in polypropylene beta crystalline substance through-thickness in photo, and with the α crystalline substance of ontology without obvious boundary Face.

Fig. 6 is the X-ray diffractogram of the polypropylene-base plate with gradient-structure prepared by the embodiment of the present invention 2.From figure In can calculate the content (k of polypropylene beta crystalline substance_β) through-thickness in concentration gradient be distributed.

Fig. 7 is that the inside crystal form of the polypropylene-base plate with gradient-structure prepared by the embodiment of the present invention 3 is distributed signal Figure.

Specific embodiment

Below in conjunction with the embodiment of the present invention, technical solution of the present invention is further clearly and completely described, Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.

Embodiment 1

(1) polypropylene-base plate is prepared

Directly homopolypropylene (T30S) pellet is pressed and molded as plate at 180 DEG C, homopolymerization poly- third is obtained after cold pressing Alkene (T30S) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Nylon66 fiber (PA66) and terres rares beta nucleater (WBG-II) 98:2 in mass ratio are subjected to ingredient, after premixing, In Melt blending extruding pelletization is carried out at 275 DEG C, then compression molding is the uniform plate of thickness at 275 DEG C, is born after cold pressing Carry terres rares beta nucleater (WBG-II)/nylon66 fiber (PA66) carrier plate that nucleating agent concentration is 2%；

(3) preparation has the polypropylene-base plate of gradient-structure

Terres rares beta nucleater (WBG-II)/nylon66 fiber (PA66) carrier plate is placed in homopolypropylene (T30S) substrate The upper layer of material, carrier board dimension are not less than polypropylene-base board dimension, and make the upper of carrier plate and polypropylene-base plate Surface fitting, forms tight contact structure, is pressed and molded, and molding temperature is 225 DEG C, clamp time 10mins, cold pressing Homopolymerization poly- third of the carrier to get the β type crystal on polypropylene-base plate thickness direction in concentration gradient structure distribution is removed afterwards Alkene (T30S) substrate material.

Resulting homopolypropylene (T30S) substrate material is subjected to shock-testing, punching along concentration gradient structure distribution direction The purer homopolypropylene of hit intensity (T30S) improves 80%, is 2% compared with being the concentration measured with homopolypropylene (T30S) The terres rares beta nucleater (WBG-II) being homogeneously distributed/homopolypropylene (T30S) improves 60%；Again by resulting homopolymerization poly- third Alkene (T30S) substrate material carries out extension test, the purer homopolypropylene of tensile strength along concentration gradient structure distribution vertical direction (T30S) 4% is improved, compared with the terres rares β nucleation being homogeneously distributed for being 2% with the concentration that homopolypropylene (T30S) is metering Agent (WBG-II)/homopolypropylene (T30S) improves 6%.

Embodiment 2

(1) polypropylene-base plate is prepared

Directly homopolypropylene (T30S) is pressed and molded as plate at 185 DEG C, obtains homopolypropylene after cold pressing (T30S) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Nylon66 fiber (PA66) and aromatic beta nucleater (TMB-5) 95:5 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 270 DEG C, then compression molding is the uniform plate of thickness at 270 DEG C, is obtained after cold pressing Load aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) carrier plate that nucleating agent concentration is 5%；

(3) preparation has the polypropylene-base plate of gradient-structure

Aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) carrier plate is placed in homopolypropylene (T30S) substrate The upper and lower of material, carrier board dimension are not less than polypropylene-base plate, and make carrier plate and polypropylene-base plate Upper and lower surfaces fitting, forms sandwich, is pressed and molded, and molding temperature is 220 DEG C, clamp time 30mins, cold pressing Homopolymerization poly- third of the carrier to get the β type crystal on polypropylene-base plate thickness direction in concentration gradient structure distribution is removed afterwards Alkene (T30S) substrate material.

Resulting homopolypropylene (T30S) substrate material is subjected to shock-testing, punching along concentration gradient structure distribution direction The purer homopolypropylene of hit intensity (T30S) improves 120%, is 5% compared with being the concentration measured with homopolypropylene (T30S) The homopolypropylene (T30S) being homogeneously distributed/aromatic beta nucleater (TMB-5) improves 102%；Resulting homopolymerization is gathered again Propylene (T30S) substrate material carries out extension test, the purer homopolypropylene of tensile strength along concentration gradient structure distribution vertical direction (T30S) 6% is improved, compared with the homopolypropylene being homogeneously distributed for being 5% with the concentration that homopolypropylene (T30S) is metering (T30S)/aromatic beta nucleater (TMB-5) improves 9%.

Embodiment 3

(1) polypropylene-base plate is prepared

Directly random polypropylene (R200P) is pressed and molded as plate at 190 DEG C, obtains random polypropylene after cold pressing (R200P) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Polyester (PET) and glucitols α nucleating agent (DBS) 90:10 in mass ratio are subjected to ingredient, after premixing, 260 Melt blending extruding pelletization is carried out at DEG C, then compression molding is the uniform plate of thickness at 260 DEG C, obtains loading into after cold pressing Glucitols α nucleating agent (DBS)/polyester (PET) carrier plate that core agent concentration is 10%；

(3) preparation has the polypropylene-base plate of gradient-structure

Aromatic glucitols α nucleating agent (DBS)/polyester (PET) carrier plate is placed in random polypropylene (R200P) The upper layer of substrate material, carrier board dimension are not less than polypropylene-base plate, and make the upper of carrier plate and polypropylene-base plate Surface fitting, forms tight contact structure, is pressed and molded, and molding temperature is 200 DEG C, clamp time 30mins, cold pressing Removing carrier afterwards to get the β type crystal on polypropylene-base plate thickness direction is in random poly- the third of concentration gradient structure distribution Alkene (R200P) substrate material.

Resulting random polypropylene (R200P) substrate material is subjected to shock-testing along concentration gradient structure distribution direction, Impact strength improves 130% compared with random polypropylene (R200P), is compared with the concentration that random polypropylene (R200P) is metering The 10% glucitols α nucleating agent (DBS) being homogeneously distributed/random polypropylene (R200P) improves 110%；It again will be resulting Random polypropylene (R200P) substrate material carries out extension test along concentration gradient structure distribution vertical direction, and tensile strength is more random Polypropylene (R200P) improves 7%, compared with the mountain being homogeneously distributed for being 10% with the concentration that random polypropylene (R200P) is metering Pears alcohols α nucleating agent (DBS)/random polypropylene (R200P) improves 10%.

Embodiment 4

(1) polypropylene-base bar is prepared

Directly homopolypropylene (T30S) is pressed and molded as bar at 190 DEG C, obtains homopolypropylene after cold pressing (T30S) base rod material；

(2) preparation load has the carrier tubing of nucleating agent

Nylon66 fiber (PA66) and aromatic beta nucleater (TMB-5) 99:1 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 265 DEG C, then compression molding is the uniform tubing of caliber at 265 DEG C, is obtained after cold pressing Load aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) carrier tubing that nucleating agent concentration is 1%；

(3) preparation has the polypropylene-base bar of gradient-structure

Homopolypropylene (T30S) bar is placed in aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) carrier tubing Sandwich layer, the internal diameter of carrier tubing is identical as the diameter of polypropylene-base bar, and makes carrier tubing and polypropylene base rod The outer surface of material is bonded, and is formed clad structure, is pressed and molded, and molding temperature is 230 DEG C, clamp time 5mins, cold pressing Remove carrier afterwards to get being in the homopolymerization poly- third of concentration gradient structure distribution along the β type crystal of polypropylene-base bar in the radial direction Alkene (T30S) base rod material.

Resulting homopolypropylene (T30S) base rod material is subjected to shock-testing, punching along concentration gradient structure distribution direction The purer homopolypropylene of hit intensity (T30S) improves 70%, is 1% compared with being the concentration measured with homopolypropylene (T30S) The aromatic beta nucleater (TMB-5) being homogeneously distributed/homopolypropylene (T30S) improves 48%；Resulting homopolymerization is gathered again Propylene (T30S) base rod material carries out extension test, the purer homopolypropylene of tensile strength along concentration gradient structure distribution vertical direction (T30S) 4% is improved, compared with the homopolypropylene being homogeneously distributed for being 1% with the concentration that homopolypropylene (T30S) is metering (T30S)/aromatic beta nucleater (TMB-5) improves 7%.

Embodiment 5

(1) polypropylene-base membrane material is prepared

Directly homopolypropylene (T30S) pellet is pressed and molded as sheet material at 180 DEG C, homopolymerization poly- third is obtained after cold pressing Alkene (T30S) base sheet；

(2) preparation load has the carrier membrane material of nucleating agent

Nylon66 fiber (PA66) and terres rares beta nucleater (WBG-II) 97:3 in mass ratio are subjected to ingredient, after premixing, In Melt blending extruding pelletization is carried out at 272 DEG C, then compression molding is the uniform membrane material of thickness at 272 DEG C, is born after cold pressing Carry terres rares beta nucleater (WBG-II)/nylon66 fiber (PA66) carrier membrane material that nucleating agent concentration is 3%；

(3) preparation has the polypropylene-base membrane material of gradient-structure

Terres rares beta nucleater (WBG-II)/nylon66 fiber (PA66) carrier membrane material is placed in homopolypropylene (T30S) basement membrane The upper and lower of material, carrier membrane material size are not less than polypropylene-base membrane material, and make carrier membrane material and polypropylene-base membrane material Upper and lower surfaces fitting, forms sandwich structure, is pressed and molded, and molding temperature is 200 DEG C, clamp time 2mins, cold pressing Homopolymerization poly- third of the carrier to get the β type crystal on polypropylene-base plate thickness direction in concentration gradient structure distribution is removed afterwards Alkene (T30S) basement membrane material.

Resulting homopolypropylene (T30S) basement membrane material is subjected to extension test along concentration gradient structure distribution vertical direction, The purer homopolypropylene of tensile strength (T30S) improves 5%, is 3% compared with being the concentration measured with homopolypropylene (T30S) The terres rares beta nucleater (WBG-II) being homogeneously distributed/homopolypropylene (T30S) improves 8%.

Embodiment 6

(1) polypropylene-base tubing is prepared

Directly homopolypropylene (T30S) is pressed and molded as tubing at 195 DEG C, obtains homopolypropylene after cold pressing (T30S) base tube material；

(2) preparation load has the carrier tubing and bar of nucleating agent

Nylon66 fiber (PA66) and aromatic beta nucleater (TMB-5) 99:1 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 270 DEG C, then compression molding is that caliber uniform tubing or diameter are identical at 270 DEG C Bar obtains aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) support tube that load nucleating agent concentration is 1% after cold pressing Material or bar；

(3) preparation has the polypropylene-base tubing of gradient-structure

Homopolypropylene (T30S) tubing is placed in aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) carrier tubing Sandwich layer, then aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) bar is placed in homopolypropylene (T30S) tubing The internal diameter of sandwich layer, carrier tubing is identical as the outer diameter of polypropylene-base tubing, and the internal diameter of polypropylene pipe and carrier bar Diameter it is identical, and carrier tubing or bar and the inner and outer surfaces of polypropylene-base tubing are fitted closely, form cladding mutually Structure is pressed and molded, and molding temperature is 235 DEG C, clamp time 1mins, and carrier is removed after cold pressing to get along polypropylene The β type crystal of base tube material in the radial direction is in homopolypropylene (T30S) base rod material of concentration gradient structure distribution.

Resulting homopolypropylene (T30S) base tube material is subjected to extension test along concentration gradient structure distribution vertical direction, The purer homopolypropylene of tensile strength (T30S) improves 4%, is 1% compared with being the concentration measured with homopolypropylene (T30S) The homopolypropylene (T30S) being homogeneously distributed/aromatic beta nucleater (TMB-5) improves 7%.

Embodiment 7

(1) polypropylene-base profile shapes is prepared

Directly homopolypropylene (T30S) is pressed and molded as profile shapes (such as five-pointed star type, ball-type, the moon at 200 DEG C Tooth form), homopolypropylene (T30S) base profile shapes is obtained after cold pressing；

(2) preparation load has the carrier membrane material of nucleating agent

Nylon66 fiber (PA66) and aromatic beta nucleater (TMB-5) 85:15 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 265 DEG C, then compression molding is the uniform membrane material of thickness at 268 DEG C, is obtained after cold pressing Load aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) carrier membrane material that nucleating agent concentration is 15%；

(3) preparation has the polypropylene-base profile shapes of gradient-structure

Aromatic beta nucleater (TMB-5)/nylon66 fiber (PA66) carrier membrane material is wrapped in homopolypropylene (T30S) is different The outer surface of profile, and carrier membrane material and the outer surface of polypropylene-base profile shapes are bonded, full clad structure is formed, mould is carried out Molded, molding temperature is 225 DEG C, clamp time 15mins, and thin-film carrier is removed after cold pressing to get along polypropylene-base appearance β type crystal in the vertical direction of face is in homopolypropylene (T30S) base profile shapes of concentration gradient structure distribution.

Embodiment 8

(1) polypropylene-base plate is prepared

Block copolymerization polypropylene (EPS30R) and glass fibre (GF) 60:40 in mass ratio are directly subjected to ingredient, melting Blending extrusion be granulated, then at 185 DEG C compression molding be plate, obtained after cold pressing concentration be 40% glass fibre (GF)/it is embedding Section copolymer polypropylene (EPS30R) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Polysulfones (PSF) and terres rares beta nucleater (WBG-II) 80:20 in mass ratio are subjected to ingredient, after premixing, In Melt blending extruding pelletization is carried out at 280 DEG C, then compression molding is the uniform plate of thickness at 280 DEG C, is born after cold pressing Carry terres rares beta nucleater (WBG-II)/polysulfones (PSF) carrier plate that nucleating agent concentration is 20%；

(3) preparation has the polypropylene-base plate of gradient-structure

It is poly- that terres rares beta nucleater (WBG-II)/polysulfones (PSF) carrier plate is placed in glass fibre (GF)/block copolymerization The upper layer of propylene (EPS30R) substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper surface of alkenyl plate is bonded, and is formed tight contact structure, is pressed and molded, and molding temperature is 230 DEG C, and clamp time is 10mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Glass fibre (GF)/block copolymerization polypropylene (EPS30R) substrate material.

By resulting glass fibre (GF)/block copolymerization polypropylene (EPS30R) substrate material along concentration gradient structure distribution side To shock-testing is carried out, impact strength improves 150% compared with glass fibre (GF)/block copolymerization polypropylene (EPS30R), compared with With glass fibre (GF)/block copolymerization polypropylene (EPS30R) be metering concentration be 20% the terres rares β being homogeneously distributed at Core agent (WBG-II)/glass fibre (GF)/block copolymerization polypropylene (EPS30R) improves 120%；Again by resulting glass fibers It ties up (GF)/block copolymerization polypropylene (EPS30R) substrate material and carries out extension test along concentration gradient structure distribution vertical direction, draw It stretches intensity and improves 30% compared with glass fibre (GF)/block copolymerization polypropylene (EPS30R), it is total compared with glass fibre (GF)/block Poly- polypropylene (EPS30R) is terres rares beta nucleater (the WBG-II)/glass fibre being homogeneously distributed that the concentration of metering is 20% (GF)/block copolymerization polypropylene (EPS30R) improves 40%.

Embodiment 9

(1) polypropylene-base plate is prepared

Homopolypropylene (T30S) and montmorillonite 95:5 in mass ratio are directly subjected to ingredient, melt blending extruding pelletization, Compression molding is plate at 170 DEG C again, and montmorillonite/homopolypropylene (T30S) substrate material that concentration is 5% is obtained after cold pressing；

(2) preparation load has the carrier plate of nucleating agent

Polycarbonate (PC) and aromatic beta nucleater (TMB-5) 92:8 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 265 DEG C, then compression molding is the uniform plate of thickness at 270 DEG C, is obtained after cold pressing Load aromatic beta nucleater (TMB-5)/carbonic ester (PC) carrier plate that nucleating agent concentration is 8%；

(3) preparation has the polypropylene-base plate of gradient-structure

Aromatic beta nucleater (TMB-5)/carbonic ester (PC) carrier plate is placed in montmorillonite/homopolypropylene (T30S) the upper and lower of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper and lower surfaces of alkenyl plate are bonded, and are formed sandwich, are pressed and molded, and molding temperature is 220 DEG C, and clamp time is 15mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Montmorillonite/homopolypropylene (T30S) substrate material.

Resulting montmorillonite/homopolypropylene (T30S) substrate material is subjected to impact survey along concentration gradient structure distribution direction Examination, impact strength improves 125% compared with montmorillonite/homopolypropylene (T30S), compared with montmorillonite/homopolypropylene (T30S) The aromatic beta nucleater (TMB-5) being homogeneously distributed/montmorillonite/homopolypropylene (T30S) that concentration for metering is 8% mentions It is high by 100%；Again by resulting montmorillonite/homopolypropylene (T30S) substrate material along concentration gradient structure distribution vertical direction into Row extension test, tensile strength improve 23% compared with montmorillonite/homopolypropylene (T30S), compared with montmorillonite/homopolypropylene (T30S) be metering concentration be 8% aromatic beta nucleater (TMB-5)/montmorillonite/homopolypropylene being homogeneously distributed (T30S) 30% is improved.

Embodiment 10

(1) polypropylene-base plate is prepared

Random polypropylene (R200P) and calcium carbonate 75:35 in mass ratio are directly subjected to ingredient, melt blending extrusion is made Grain, then compression molding is plate at 195 DEG C, and calcium carbonate/random polypropylene (R200P) base that concentration is 35% is obtained after cold pressing Plate；

(2) preparation load has the carrier plate of nucleating agent

Polyphenylene sulfide (PPS) and metal carboxylate nucleating agent (HHPA) 90:10 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 270 DEG C, then compression molding is the uniform plate of thickness at 270 DEG C, is obtained after cold pressing Load metal carboxylate nucleating agent (HHPA)/polyphenylene sulfide (PPS) carrier plate that nucleating agent concentration is 10%；

(3) preparation has the polypropylene-base plate of gradient-structure

Metal carboxylate nucleating agent (HHPA)/polyphenylene sulfide (PPS) carrier plate is placed in calcium carbonate/random polypropylene (R200P) the upper and lower of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper and lower surfaces of alkenyl plate are bonded, and are formed sandwich, are pressed and molded, and molding temperature is 210 DEG C, and clamp time is 20mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Calcium carbonate/random polypropylene (R200P) substrate material.

Resulting calcium carbonate/random polypropylene (R200P) substrate material is impacted along concentration gradient structure distribution direction Test, impact strength improves 110% compared with calcium carbonate/random polypropylene (R200P), compared with calcium carbonate/random polypropylene (R200P) be metering concentration be 10% metal carboxylate nucleating agent (HHPA)/calcium carbonate/random polypropylene being homogeneously distributed (R200P) 95% is improved；Again by resulting calcium carbonate/random polypropylene (R200P) substrate material along concentration gradient structure distribution Vertical direction carries out extension test, and tensile strength improves 25% compared with calcium carbonate/random polypropylene (R200P), compared with calcium carbonate/ Random polypropylene (R200P) is metal carboxylate nucleating agent (HHPA)/calcium carbonate/nothing being homogeneously distributed that the concentration of metering is 10% Isotactic polypropylene (R200P) improves 33%.

Embodiment 11

(1) polypropylene-base plate is prepared

Block copolymerization polypropylene (EPS30R) and graphene 90:10 in mass ratio are directly subjected to ingredient, melt blending squeezes It is granulated out, then compression molding is plate at 200 DEG C, graphene/block copolymerization polypropylene that concentration is 10% is obtained after cold pressing (EPS30R) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Nylon66 fiber (PA66) and Sorbitol Nucleator sorbierite (DMDBS) 99:1 in mass ratio are subjected to ingredient, premix After conjunction, melt blending extruding pelletization is carried out at 265 DEG C, then compression molding is the uniform plate of thickness at 265 DEG C, after cold pressing Obtain Sorbitol Nucleator sorbierite (DMDBS)/nylon66 fiber (PA66) carrier plate that load nucleating agent concentration is 1%；

(3) preparation has the polypropylene-base plate of gradient-structure

Sorbitol Nucleator sorbierite (DMDBS)/nylon66 fiber (PA66) carrier plate is placed in graphene/block copolymerization The upper layer of polypropylene (EPS30R) substrate material, carrier board dimension are not less than polypropylene-base plate, and make carrier plate and gather The upper surface of propylene substrate material is bonded, and is formed tight contact structure, is pressed and molded, and molding temperature is 205 DEG C, clamp time For 30mins, carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction in concentration gradient structure point Graphene/block copolymerization polypropylene (EPS30R) substrate material of cloth.

Resulting graphene/block copolymerization polypropylene (EPS30R) substrate material is carried out along concentration gradient structure distribution direction Shock-testing, impact strength improve 75% compared with graphene/block copolymerization polypropylene (EPS30R), compared with graphene/block Copolymer polypropylene (EPS30R) is Sorbitol Nucleator sorbierite (the DMDBS)/stone being homogeneously distributed that the concentration of metering is 1% Black alkene/block copolymerization polypropylene (EPS30R) improves 50%；Again by resulting graphene/block copolymerization polypropylene (EPS30R) Substrate material carries out extension test along concentration gradient structure distribution vertical direction, and tensile strength is compared with graphene/block copolymerization polypropylene (EPS30R) improve 16%, compared with the concentration that graphene/block copolymerization polypropylene (EPS30R) is metering is 1% homogeneous point The Sorbitol Nucleator sorbierite (DMDBS) of cloth/graphene/block copolymerization polypropylene (EPS30R) improves 25%.

Embodiment 12

(1) polypropylene-base plate is prepared

Homopolypropylene (T30S) and carbon fiber (CF) 75:25 in mass ratio are directly subjected to ingredient, melt blending squeezes out It is granulated, then compression molding is plate at 185 DEG C, carbon fiber (CF)/homopolypropylene that concentration is 25% is obtained after cold pressing (T30S) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Polyester (PET) and aromatic nucleating agent (TMC-306) 99.5:0.5 in mass ratio are subjected to ingredient, premixing Afterwards, melt blending extruding pelletization is carried out at 270 DEG C, then compression molding is the uniform plate of thickness at 270 DEG C, after cold pressing Aromatic nucleating agent (TMC-306)/polyester (PET) the carrier plate for being 0.5% to load nucleating agent concentration；

(3) preparation has the polypropylene-base plate of gradient-structure

Aromatic nucleating agent (TMC-306)/polyester (PET) carrier plate is placed in carbon fiber (CF)/homopolypropylene (T30S) the upper and lower of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper and lower surfaces of alkenyl plate are bonded, and are formed sandwich, are pressed and molded, and molding temperature is 200 DEG C, and clamp time is 45mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Carbon fiber (CF)/homopolypropylene (T30S) substrate material.

Resulting carbon fiber (CF)/homopolypropylene (T30S) substrate material is rushed along concentration gradient structure distribution direction Test is hit, impact strength improves 60% compared with carbon fiber (CF)/homopolypropylene (T30S), compared with carbon fiber (CF)/homopolymerization Polypropylene (T30S) is aromatic nucleating agent (the TMC-306)/carbon fiber being homogeneously distributed that the concentration of metering is 0.5% (CF)/homopolypropylene (T30S) improves 45%；Again by resulting carbon fiber (CF)/homopolypropylene (T30S) substrate material edge Concentration gradient structure distribution vertical direction carries out extension test, and tensile strength is mentioned compared with carbon fiber (CF)/homopolypropylene (T30S) It is high by 13%, compared be the aromatic series being homogeneously distributed that the concentration measured is 0.5% with carbon fiber (CF)/homopolypropylene (T30S) Class nucleating agent (TMC-306)/carbon fiber (CF)/homopolypropylene (T30S) improves 23%.

Embodiment 13

(1) polypropylene-base plate is prepared

Random polypropylene (R200P) and glass fibre (GF) 70:30 in mass ratio are directly subjected to ingredient, melt blending squeezes It is granulated out, then compression molding is plate at 180 DEG C, glass fibre (GF)/random poly- third that concentration is 30% is obtained after cold pressing Alkene (R200P) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Polysulfones (PSF) and phosphoric acid salt nucleating agent (NA-11) 99.9:0.1 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 200 DEG C, then compression molding is the uniform plate of thickness at 200 DEG C, is obtained after cold pressing Load phosphoric acid salt nucleating agent (NA-11)/polysulfones (PSF) carrier plate that nucleating agent concentration is 0.1%；

(3) preparation has the polypropylene-base plate of gradient-structure

Phosphoric acid salt nucleating agent (NA-11)/polysulfones (PSF) carrier plate is placed in glass fibre (GF)/random polypropylene (R200P) the upper and lower of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper and lower surfaces of alkenyl plate are bonded, and are formed sandwich, are pressed and molded, and molding temperature is 195 DEG C, and clamp time is 60mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Glass fibre (GF)/random polypropylene (R200P) substrate material.

By resulting glass fibre (GF)/random polypropylene (R200P) substrate material along concentration gradient structure distribution direction into Row shock-testing, impact strength improves 50% compared with glass fibre (GF)/random polypropylene (R200P), compared with glass fibre (GF)/random polypropylene (R200P) is phosphoric acid salt nucleating agent (the NA-11)/glass being homogeneously distributed that the concentration of metering is 0.1% Glass fiber (GF)/random polypropylene (R200P) improves 42%；Again by resulting glass fibre (GF)/random polypropylene (R200P) substrate material carries out extension test along concentration gradient structure distribution vertical direction, and tensile strength is compared with glass fibre (GF)/nothing Isotactic polypropylene (R200P) improves 10%, is compared with the concentration that glass fibre (GF)/random polypropylene (R200P) is metering The 0.1% phosphoric acid salt nucleating agent (NA-11) being homogeneously distributed/glass fibre (GF)/random polypropylene (R200P) improves 20%.

Embodiment 14

(1) polypropylene-base plate is prepared

Block copolymerization polypropylene (EPS30R) and talcum powder 65:35 in mass ratio are directly subjected to ingredient, melt blending squeezes It is granulated out, then compression molding is plate at 190 DEG C, talcum powder/block copolymerization polypropylene that concentration is 35% is obtained after cold pressing (EPS30R) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Polycarbonate (PC) and dibenzal sorbitol (DBS) 90:10 in mass ratio are subjected to ingredient, after premixing, 260 Melt blending extruding pelletization is carried out at DEG C, then compression molding is the uniform plate of thickness at 260 DEG C, obtains loading into after cold pressing Dibenzal sorbitol (DBS)/polycarbonate (PC) carrier plate that core agent concentration is 10%；

(3) preparation has the polypropylene-base plate of gradient-structure

Dibenzal sorbitol (DBS)/polycarbonate (PC) carrier plate is placed in talcum powder/block copolymerization polypropylene (EPS30R) upper layer of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and polypropylene-base The upper surface of plate is bonded, and is formed tight contact structure, is pressed and molded, and molding temperature is 190 DEG C, and clamp time is 80mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Talcum powder/block copolymerization polypropylene (EPS30R) substrate material.

Resulting talcum powder/block copolymerization polypropylene (EPS30R) substrate material is carried out along concentration gradient structure distribution direction Shock-testing, impact strength improve 100% compared with talcum powder/block copolymerization polypropylene (EPS30R), compared with talcum powder/block Copolymer polypropylene (EPS30R) is dibenzal sorbitol (DBS)/talcum powder/block being homogeneously distributed that the concentration of metering is 10% Copolymer polypropylene (EPS30R) improves 80%；Again by resulting talcum powder/block copolymerization polypropylene (EPS30R) substrate material edge Concentration gradient structure distribution vertical direction carries out extension test, and tensile strength is compared with talcum powder/block copolymerization polypropylene (EPS30R) 23% is improved, compared with two be homogeneously distributed for being 10% with the concentration that talcum powder/block copolymerization polypropylene (EPS30R) is metering Benzylidene sorbitol (DBS)/talcum powder/block copolymerization polypropylene (EPS30R) improves 31%.

Embodiment 15

(1) polypropylene-base plate is prepared

Homopolypropylene (T30S) and calcium carbonate 60:40 in mass ratio are directly subjected to ingredient, melt blending extruding pelletization, Compression molding is plate at 195 DEG C again, and calcium carbonate/homopolypropylene (T30S) substrate that concentration is 40% is obtained after cold pressing Material；

(2) preparation load has the carrier plate of nucleating agent

Polyphenylene sulfide (PPS) and aromatic nucleating agent (TMB-5) 92:8 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 290 DEG C, then compression molding is the uniform plate of thickness at 270 DEG C, is obtained after cold pressing Load aromatic nucleating agent (TMB-5)/polyphenylene sulfide (PPS) carrier plate that nucleating agent concentration is 8%；

(3) preparation has the polypropylene-base plate of gradient-structure

Aromatic nucleating agent (TMB-5)/polyphenylene sulfide (PPS) carrier plate is placed in calcium carbonate/homopolypropylene (T30S) the upper and lower of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper and lower surfaces of alkenyl plate are bonded, and are formed sandwich, are pressed and molded, and molding temperature is 195 DEG C, and clamp time is 100mins removes carrier to get the β type crystal on polypropylene-base plate thickness direction in concentration gradient structure point after cold pressing Calcium carbonate/homopolypropylene (T30S) substrate material of cloth.

Resulting calcium carbonate/homopolypropylene (T30S) substrate material is subjected to impact survey along concentration gradient structure distribution direction Examination, impact strength improves 95% compared with calcium carbonate/homopolypropylene (T30S), compared with calcium carbonate/homopolypropylene (T30S) The aromatic nucleating agent (TMB-5) being homogeneously distributed/calcium carbonate/homopolypropylene (T30S) that concentration for metering is 8% mentions It is high by 70%；Again by resulting calcium carbonate/homopolypropylene (T30S) substrate material along concentration gradient structure distribution vertical direction into Row extension test, tensile strength improve 21% compared with calcium carbonate/homopolypropylene (T30S), compared with calcium carbonate/homopolypropylene (T30S) be metering concentration be 8% aromatic nucleating agent (TMB-5)/calcium carbonate/homopolypropylene being homogeneously distributed (T30S) 30% is improved.

Embodiment 16

(1) polypropylene-base plate is prepared

Random polypropylene (R200P) and graphene 90:10 in mass ratio are directly subjected to ingredient, melt blending extrusion is made Grain, then compression molding is plate at 200 DEG C, and graphene/random polypropylene (R200P) base that concentration is 10% is obtained after cold pressing Plate；

(2) preparation load has the carrier plate of nucleating agent

Nylon66 fiber (PA66) and terres rares beta nucleater (WBG-II) 87:13 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 270 DEG C, then compression molding is the uniform plate of thickness at 215 DEG C, is obtained after cold pressing Load terres rares beta nucleater (WBG-II)/nylon66 fiber (PA66) carrier plate that nucleating agent concentration is 13%；

(3) preparation has the polypropylene-base plate of gradient-structure

Terres rares beta nucleater (WBG-II)/nylon66 fiber (PA66) carrier plate is placed in graphene/random polypropylene (R200P) the upper and lower of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper and lower surfaces of alkenyl plate are bonded, and are formed sandwich, are pressed and molded, and molding temperature is 180 DEG C, and clamp time is 120mins removes carrier to get the β type crystal on polypropylene-base plate thickness direction in concentration gradient structure point after cold pressing Graphene/random polypropylene (R200P) substrate material of cloth.

Resulting graphene/random polypropylene (R200P) substrate material is impacted along concentration gradient structure distribution direction Test, impact strength improves 110% compared with graphene/random polypropylene (R200P), compared with graphene/random polypropylene (R200P) be metering concentration be 13% terres rares beta nucleater (WBG-II)/graphene/random polypropylene being homogeneously distributed (R200P) 78% is improved；Again by resulting graphene/random polypropylene (R200P) substrate material along concentration gradient structure distribution Vertical direction carries out extension test, and tensile strength improves 28% compared with graphene/random polypropylene (R200P), compared with graphene/ Random polypropylene (R200P) be metering concentration be 13% terres rares beta nucleater (the WBG-II)/graphene being homogeneously distributed/ Random polypropylene (R200P) improves 34%.

Embodiment 17

(1) polypropylene-base plate is prepared

Block copolymerization polypropylene (EPS30R) and carbon fiber (CF) 93:7 in mass ratio are directly subjected to ingredient, melt blending Extruding pelletization, then compression molding is plate at 195 DEG C, and it is poly- that carbon fiber (CF)/block copolymerization that concentration is 7% is obtained after cold pressing Propylene (EPS30R) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Polyester (PET) and phosphoric acid salt nucleating agent (NA-10) 93:7 in mass ratio are subjected to ingredient, after premixing, 270 Melt blending extruding pelletization is carried out at DEG C, then compression molding is the uniform plate of thickness at 265 DEG C, obtains loading into after cold pressing Phosphoric acid salt nucleating agent (NA-10)/polyester (PET) carrier plate that core agent concentration is 7%；

(3) preparation has the polypropylene-base plate of gradient-structure

Phosphoric acid salt nucleating agent (NA-10)/polyester (PET) carrier plate is placed in carbon fiber (CF)/block copolymerization poly- third The upper layer of alkene (EPS30R) substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and polypropylene The upper surface of substrate material is bonded, and is formed tight contact structure, is pressed and molded, and molding temperature is 225 DEG C, and clamp time is 65mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Carbon fiber (CF)/block copolymerization polypropylene (EPS30R) substrate material.

By resulting carbon fiber (CF)/block copolymerization polypropylene (EPS30R) substrate material along concentration gradient structure distribution direction Shock-testing is carried out, impact strength improves 130% compared with carbon fiber (CF)/block copolymerization polypropylene (EPS30R), compared with carbon Fiber (CF)/block copolymerization polypropylene (EPS30R) is the phosphoric acid salt nucleating agent being homogeneously distributed that the concentration of metering is 7% (NA-10)/carbon fiber (CF)/block copolymerization polypropylene (EPS30R) improves 121%；Again by resulting carbon fiber (CF)/embedding Section copolymer polypropylene (EPS30R) substrate material carries out extension test along concentration gradient structure distribution vertical direction, and tensile strength is compared with carbon Fiber (CF)/block copolymerization polypropylene (EPS30R) improves 31%, compared with carbon fiber (CF)/block copolymerization polypropylene It (EPS30R) is that the phosphoric acid salt nucleating agent (NA-10) being homogeneously distributed/carbon fiber (CF)/block that the concentration measured is 7% is total Poly- polypropylene (EPS30R) improves 37%.

Embodiment 18

(1) polypropylene-base plate is prepared

Homopolypropylene (T30S) and glass fibre (GF) 97:3 in mass ratio are directly subjected to ingredient, melt blending squeezes out It is granulated, then compression molding is plate at 190 DEG C, glass fibre (GF)/homopolypropylene that concentration is 3% is obtained after cold pressing (T30S) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Polysulfones (PSF) and aromatic beta nucleater (TMB-5) 85:15 in mass ratio are subjected to ingredient, after premixing, In Melt blending extruding pelletization is carried out at 250 DEG C, then compression molding is the uniform plate of thickness at 200 DEG C, is born after cold pressing Carry aromatic beta nucleater (TMB-5)/polysulfones (PSF) carrier plate that nucleating agent concentration is 5%；

(3) preparation has the polypropylene-base plate of gradient-structure

Aromatic beta nucleater (TMB-5)/polysulfones (PSF) carrier plate is placed in glass fibre (GF)/homopolypropylene (T30S) the upper and lower of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper and lower surfaces of alkenyl plate are bonded, and are formed sandwich, are pressed and molded, and molding temperature is 230 DEG C, and clamp time is 30mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Glass fibre (GF)/homopolypropylene (T30S) substrate material.

Resulting glass fibre (GF)/homopolypropylene (T30S) substrate material is carried out along concentration gradient structure distribution direction Shock-testing, impact strength improves 130% compared with glass fibre (GF)/homopolypropylene (T30S), compared with glass fibre (GF)/homopolypropylene (T30S) is aromatic beta nucleater (the TMB-5)/glass being homogeneously distributed that the concentration of metering is 5% Fiber (GF)/homopolypropylene (T30S) improves 110%；Again by resulting glass fibre (GF)/homopolypropylene (T30S) Substrate material carries out extension test along concentration gradient structure distribution vertical direction, and tensile strength is compared with glass fibre (GF)/homopolymerization poly- third Alkene (T30S) improves 30%, compared with the concentration that glass fibre (GF)/homopolypropylene (T30S) is metering is 5% homogeneous point The aromatic beta nucleater (TMB-5) of cloth/glass fibre (GF)/homopolypropylene (T30S) improves 35%.

Embodiment 19

(1) polypropylene-base plate is prepared

Random polypropylene (R200P) and montmorillonite 95:5 in mass ratio are directly subjected to ingredient, melt blending extruding pelletization, Compression molding is plate at 185 DEG C again, and montmorillonite/random polypropylene (R200P) substrate that concentration is 5% is obtained after cold pressing Material；

(2) preparation load has the carrier plate of nucleating agent

Polycarbonate (PC) and terres rares beta nucleater (WBG-II) 90:10 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 230 DEG C, then compression molding is the uniform plate of thickness at 215 DEG C, is obtained after cold pressing Load terres rares beta nucleater (WBG-II)/polycarbonate (PC) carrier plate that nucleating agent concentration is 10%；

(3) preparation has the polypropylene-base plate of gradient-structure

Terres rares beta nucleater (WBG-II)/polycarbonate (PC) carrier plate is placed in montmorillonite/random polypropylene (R200P) the upper and lower of substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and poly- third The upper and lower surfaces of alkenyl plate are bonded, and are formed sandwich, are pressed and molded, and molding temperature is 240 DEG C, and clamp time is 5mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Montmorillonite/random polypropylene (R200P) substrate material.

Resulting montmorillonite/random polypropylene (R200P) substrate material is impacted along concentration gradient structure distribution direction Test, impact strength improves 130% compared with montmorillonite/random polypropylene (R200P), compared with montmorillonite/random polypropylene (R200P) be metering concentration be 10% terres rares beta nucleater (WBG-II)/montmorillonite/random polypropylene being homogeneously distributed (R200P) 110% is improved；Again by resulting montmorillonite/random polypropylene (R200P) substrate material along concentration gradient structure distribution Vertical direction carries out extension test, and tensile strength improves 30% compared with montmorillonite/random polypropylene (R200P), compared with montmorillonite/ Random polypropylene (R200P) be metering concentration be 10% terres rares beta nucleater (the WBG-II)/montmorillonite being homogeneously distributed/ Random polypropylene (R200P) improves 35%.

Embodiment 20

(1) polypropylene-base plate is prepared

Block copolymerization polypropylene (EPS30R) and calcium carbonate 85:15 in mass ratio are directly subjected to ingredient, melt blending squeezes It is granulated out, then compression molding is plate at 180 DEG C, talcum powder/block copolymerization polypropylene that concentration is 15% is obtained after cold pressing (EPS30R) substrate material；

(2) preparation load has the carrier plate of nucleating agent

Polyphenylene sulfide (PPS) and phosphoric acid salt nucleating agent (NA-10) 99:1 in mass ratio are subjected to ingredient, after premixing, Melt blending extruding pelletization is carried out at 240 DEG C, then compression molding is the uniform plate of thickness at 225 DEG C, is obtained after cold pressing Load phosphoric acid salt nucleating agent (NA-10)/polyphenylene sulfide (PPS) carrier plate that nucleating agent concentration is 1%；

(3) preparation has the polypropylene-base plate of gradient-structure

Phosphoric acid salt nucleating agent (NA-10)/polyphenylene sulfide (PPS) carrier plate is placed in talcum powder/block copolymerization poly- third The upper layer of alkene (EPS30R) substrate material, carrier board dimension is not less than polypropylene-base plate, and makes carrier plate and polypropylene The upper surface of substrate material is bonded, and is formed tight contact structure, is pressed and molded, and molding temperature is 220 DEG C, and clamp time is 50mins, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get the β type crystal on polypropylene-base plate thickness direction Talcum powder/block copolymerization polypropylene (EPS30R) substrate material.

Resulting talcum powder/block copolymerization polypropylene (EPS30R) substrate material is carried out along concentration gradient structure distribution direction Shock-testing, impact strength improve 80% compared with talcum powder/block copolymerization polypropylene (EPS30R), compared with talcum powder/block Copolymer polypropylene (EPS30R) be metering concentration be 1% phosphoric acid salt nucleating agent (the NA-10)/talcum powder being homogeneously distributed/ Block copolymerization polypropylene (EPS30R) improves 74%；Again by resulting talcum powder/block copolymerization polypropylene (EPS30R) substrate Material carries out extension test along concentration gradient structure distribution vertical direction, and tensile strength is compared with talcum powder/block copolymerization polypropylene (EPS30R) improve 20%, compared with the concentration that talcum powder/block copolymerization polypropylene (EPS30R) is metering is 1% homogeneous point The phosphoric acid salt nucleating agent (NA-10) of cloth/talcum powder/block copolymerization polypropylene (EPS30R) improves 33%.

Comparative example 1

Directly homopolypropylene (T30S) pellet is pressed and molded at 225 DEG C, clamp time 10mins is obtained after cold pressing Homopolypropylene (T30S) substrate material,

Resulting homopolypropylene (T30S) substrate material is subjected to impact and extension test, impact strength 4.45kJ/ m², yield strength 30.2MPa.

Comparative example 2

Homopolypropylene (T30S) and terres rares beta nucleater (WBG-II) 98:2 in mass ratio are directly subjected to ingredient, melted Melt blending extrusion granulation, then be pressed and molded at 225 DEG C, clamp time 10mins, the terres rares that concentration is 2% is obtained after cold pressing Beta nucleater (WBG-II)/homopolypropylene (T30S) substrate material,

Resulting terres rares beta nucleater (WBG-II)/homopolypropylene (T30S) substrate material is impacted and is stretched survey Examination, impact strength 5.01kJ/m², yield strength 29.6MPa.

Comparative example 3

Directly random polypropylene (R200P) pellet is pressed and molded at 200 DEG C, clamp time 30mins, after cold pressing To random polypropylene (R200P) substrate material,

Resulting random polypropylene (R200P) substrate material is subjected to impact and extension test, impact strength 3.36kJ/ m², yield strength 26.5MPa.

Comparative example 4

Random polypropylene (R200P) and glucitols α nucleating agent (DBS) 90:10 in mass ratio are directly subjected to ingredient, melted Melt blending extrusion granulation, then be pressed and molded at 200 DEG C, clamp time 30mins, the sorb that concentration is 10% is obtained after cold pressing Alcohols α nucleating agent (DBS)/random polypropylene (R200P) substrate material,

Resulting glucitols α nucleating agent (DBS)/random polypropylene (R200P) substrate material is impacted and is stretched survey Examination, impact strength 3.68kJ/m², yield strength 25.8MPa.

The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain Lid is within protection scope of the present invention.Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. a kind of polypropylene-base polymer gradient functional material, it is characterised in that be by α or beta crystal-type nucleater in polypropylene-base It is spread in a certain direction under material molten state, form α or β type crystal when the molding of polypropylene-base material is in concentration in the direction A kind of function-graded material of gradient distribution；

Its step of preparation process is as follows:

(1) polypropylene base is prepared

In the form of polypropylene or polypropylene and auxiliary material mix, melt blending extruding pelletization according to a conventional method, then be molded into Type obtains polypropylene base,

(2) preparation load has the carrier of nucleating agent

Melting temperature is greater than polyacrylic high molecular polymer and α or beta crystal-type nucleater ingredient, according to a conventional method melt blending Extruding pelletization, then be pressed and molded to obtain the carrier that load has nucleating agent,

(3) preparation has the polypropylene-base material of gradient-structure

Step (2) resulting vehicle is fitted in the one side or the multi-lateral of the outer surface of polypropylene base obtained by step (1), is molded Molding, it is in concentration gradient structure distribution that carrier is removed after cold pressing to get α the or β type crystal on carrier binding face direction Polypropylene-base material, as polypropylene-base polymer gradient functional material,

The temperature setting of the compression molding is higher than the melting temperature of polypropylene base, lower than the high score that load has nucleation agent carrier The melting temperature of sub- polymer, clamp time setting are not less than 10s.

2. polypropylene-base polymer gradient functional material according to claim 1, it is characterised in that poly- third described in step (1) Alkene is any one of homopolypropylene, block copolymerization polypropylene or random polypropylene.

3. polypropylene-base polymer gradient functional material according to claim 1 or claim 2, it is characterised in that described in step (2) It is any in nylon, polyester, polysulfones, polycarbonate or polyphenylene sulfide that melting temperature, which is greater than polyacrylic high molecular polymer, Kind.

4. polypropylene-base polymer gradient functional material according to claim 1 or claim 2, it is characterised in that step (2) α or Beta crystal-type nucleater be dibenzyl sorbitol class nucleating agent, substituted aromatic heterocyclic phosphate class nucleating agent, organic carboxyl acid salt at Any one of core agent, rare earth compound class beta crystal-type nucleater or aromatic series diamide nucleating agent.

5. polypropylene-base polymer gradient functional material according to claim 4, it is characterised in that the dibenzylidene sorb Alcohols nucleating agent be dibenzal sorbitol, two (to methyl benzylidene) sorbierites, two (to ethyl benzylidene) sorbierites or Two (3,4- dimethylbenzylidene) sorbierites；The substituted aromatic heterocyclic phosphate class nucleating agent is to (4- tert-butyl benzene oxygen Base) phosphate or bis- (the 2,4- di-t-butyl phenoxy group) phosphate of methyl；The organic carboxyl acid salt nucleating agent is bis- (to tertiary fourth Yl benzoic acid) hydroxyl aluminium salt or hexahydro-phthalic acid salt；The rare earth compound class beta crystal-type nucleater is appointed for WBG series One beta crystal-type nucleater；The aromatic series diamide nucleating agent is any nucleating agent of TM series.

6. polypropylene-base polymer gradient functional material according to claim 1 or claim 2, it is characterised in that step (3) molding temperature At 180 DEG C~240 DEG C, clamp time is controlled in 1min~2h for degree control.

7. polypropylene-base polymer gradient functional material according to claim 5, it is characterised in that step (3) molding temperature control At 180 DEG C~240 DEG C, clamp time is controlled in 1min~2h system.