CN103113731B - A kind of Modification of kaolin polycaprolactone composite material and preparation method thereof - Google Patents
A kind of Modification of kaolin polycaprolactone composite material and preparation method thereof Download PDFInfo
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- CN103113731B CN103113731B CN201310054432.6A CN201310054432A CN103113731B CN 103113731 B CN103113731 B CN 103113731B CN 201310054432 A CN201310054432 A CN 201310054432A CN 103113731 B CN103113731 B CN 103113731B
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The present invention provides a kind of Modification of kaolin polycaprolactone composite material, is be prepared from by mixing, melt extruding with modified kaolin, polycaprolactone grafted maleic anhydride and antioxidant by polycaprolactone.Present invention modified kaolin by reference and polycaprolactone grafted maleic anhydride improve the mechanical property of polycaprolactone, substantially increase intensity and the thermostability of composite so that the composite prepared has the performances such as good intensity, toughness, thermostability concurrently simultaneously.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of Modification of kaolin polycaprolactone composite material and preparation method thereof.
Background technology
Polycaprolactone (PCL) is the thermoplastic of a kind of microbial degradation type, the biological degradability good with it and good mechanical property obtain the extensive concern of scientific circles and industrial quarters, are applied to realizing controlled-release pharmaceutical carrier, cell, tissue culture's pedestal；Wholly-degradable Plastic stitching thread；The thread article shaped of thin film of high intensity；Plastics low temperature impact properties modifying agent and plasticizer；Medical Modeling Material, industry, art modelling material, toy, toner, hot copying ink adhesive agent, PUR mixture etc..
But polycaprolactone is compared with current industrial wide variety of petroleum base engineering plastics, its intensity and toughness are relatively poor, thus greatly limit its range of application, therefore PCL is modified improve its serviceability be necessary, wherein the method for blending and modifying is easiest to realize, but it is fewer at present it to be carried out the report of property modification.
Summary of the invention
It is an object of the invention to provide a kind of Modification of kaolin polycaprolactone composite material and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of Modification of kaolin polycaprolactone composite material, is made up of following compositions in weight percentage:
Polycaprolactone 80-90 part
Modified kaolin 5-20 part
Polycaprolactone grafted maleic anhydride 3-8 part
Antioxidant 0.1-5 part
Described polycaprolactone is linear polycaprolactone, and its weight average molecular weight is 10000-100000g/mol.
Described modified kaolin is made up of for 15-20:5-10:40-50 in mass ratio stearic acid, Cetyltrimethylammonium bromide and Kaolin.
The percent grafting of described polycaprolactone grafted maleic anhydride is 0.3%-2%.
Antioxidant is three (2,4-di-t-butyl) phenyl-phosphite (be called for short Irganox168), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (be called for short Irganox1010), 1,3,5-trimethyl-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) at least one in benzene (being called for short Irganox1330).
A kind of method preparing above-mentioned Modification of kaolin polycaprolactone composite material, comprises the following steps:
(1) in mass ratio, stearic acid is added in aqueous solution be made up of Cetyltrimethylammonium bromide and Kaolin, heated and stirred, sucking filtration, washing, dry and to obtain modified kaolin；
(2) weigh dry polycaprolactone, polycaprolactone grafted maleic anhydride and antioxidant by proportioning, and stirred 10～12 minutes by high-speed mixer, form mixed material；
(3) mixed material in (2) is put in the hopper of double screw extruder, through frit reaction, adding, by the mode that position, side is reinforced, the dry modified kaolin prepared through (1) at its 3rd district, the 4th district or the 5th place of district, then extrusion, pelletize obtain Modification of kaolin polycaprolactone composite material.
The screw speed of described double screw extruder is 120～180r/min, each district temperature is district's temperature 70～100 DEG C, two district's temperature 160～190 DEG C, three district's temperature 170～200 DEG C, four district's temperature 160～200 DEG C, five district's temperature 160～200 DEG C, six district's temperature 160～200 DEG C, head temperature 150～190 DEG C
The present invention has following beneficial effect:
1, in the PCL course of processing, modified kaolin and polycaprolactone grafted maleic anhydride improve the mechanical property of polycaprolactone to the present invention by reference, substantially increase intensity and the thermostability of composite so that the composite prepared has the performances such as good intensity, toughness, thermostability concurrently simultaneously.
2, calcined kaolin dispersibility in high polymer after perstearic acid, Cetyltrimethylammonium bromide modification improves, and reduces and reunites, thus strengthening the adhesion strength of inorganic particulate and matrix；
3, the addition of polycaprolactone grafting horse rice anhydride (PCL-g-MAH) can either reduce inorganic particulate reunion in high polymer, function served as bridge is played again between organic polymer, form the interface transition layer of modulus gradient, produce good modified synergic effect with Kaolin, improve composite materials property and thermostability.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention done a detailed elaboration.
In each embodiment following, polycaprolactone is linear polycaprolactone, and its weight average molecular weight is 10000-100000g/mol.
Polycaprolactone grafted maleic anhydride (PCL-g-MAH) percent grafting is 0.3%-2%.
Antioxidant is the three (2 of BASF AG, 4-di-t-butyl) phenyl-phosphite (be called for short Irganox168), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (being called for short Irganox1010) and 1,3,5-trimethyl-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) at least one in benzene (being called for short Irganox1330).
The modified kaolin used in following embodiment is in mass ratio for 15-20:5-10:40-50, is added to by stearic acid in aqueous solution be made up of Cetyltrimethylammonium bromide and Kaolin, heated and stirred, sucking filtration, washing, dries and to obtain modified kaolin；Wherein stearic acid makes kaolin surface organise as modifying agent.
Polycaprolactone and modified kaolin are to need first drying to process, and polycaprolactone generally to dry drying 8 hours at 80 DEG C；Modified kaolin is dry at 90 DEG C dries 10 hours.
Embodiment 1
Weigh polycaprolactone 90 parts, modified kaolin 7 parts, polycaprolactone grafted maleic anhydride 3 parts, Irganox168 are 0.5 part, and they are stirred 10 minutes by high-speed mixer, form mixed material；Being put into by aforementioned mixture material in the hopper of double screw extruder, through frit reaction, add modified kaolin at the 3rd place of district by the mode that position, side is reinforced, then extrude, pelletize obtains Modification of kaolin polycaprolactone composite material.Wherein double screw extruder one district temperature 80 DEG C, two district's temperature 170 DEG C, three district's temperature 180 DEG C, four district's temperature 170 DEG C, five district's temperature 180 DEG C, six district's temperature 180 DEG C, head temperature 180 DEG C, screw speed is 160r/min.
Embodiment 2
Weigh polycaprolactone 80 parts, modified kaolin 12 parts, polycaprolactone grafted maleic anhydride 8 parts, Irganox168 are 0.5 part, and Irganox1330 is 4.5 parts, and they is stirred 12 minutes by high-speed mixer, forms mixed material；Being put into by aforementioned mixture material in the hopper of double screw extruder, through frit reaction, add modified kaolin at the 4th place of district by the mode that position, side is reinforced, then extrude, pelletize obtains Modification of kaolin polycaprolactone composite material；Wherein district's temperature 70 C of double screw extruder, two district's temperature 160 DEG C, three district's temperature 170 DEG C, four district's temperature 160 DEG C, five district's temperature 160 DEG C, six district's temperature 160 DEG C, head temperature 150 DEG C, screw speed is 120r/min.
Embodiment 3
Weigh polycaprolactone 80 parts, modified kaolin 15 parts, polycaprolactone grafted maleic anhydride 5 parts, Irganox1010 are 0.1 part, and they are stirred 10 minutes by high-speed mixer, form mixed material；Being put into by aforementioned mixture material in the hopper of double screw extruder, through frit reaction, add modified kaolin at the 3rd place of district by the mode that position, side is reinforced, then extrude, pelletize obtains Modification of kaolin polycaprolactone composite material；Wherein double screw extruder one district temperature 80 DEG C, two district's temperature 170 DEG C, three district's temperature 180 DEG C, four district's temperature 170 DEG C, five district's temperature 180 DEG C, six district's temperature 180 DEG C, head temperature 180 DEG C, screw speed is 180r/min.
Embodiment 4
Weigh polycaprolactone 82 parts, modified kaolin 13 parts, polycaprolactone grafted maleic anhydride 5 parts, Irganox168 be 0.2 part, Irganox1010 be 2 parts, and they stirred 10 minutes by high-speed mixer, form mixed material；Being put into by aforementioned mixture material in the hopper of double screw extruder, through frit reaction, add modified kaolin at the 5th place of district by the mode that position, side is reinforced, then extrude, pelletize obtains Modification of kaolin polycaprolactone composite material；Wherein double screw extruder one district temperature 100 DEG C, two district's temperature 190 DEG C, three district's temperature 200 DEG C, four district's temperature 200 DEG C, five district's temperature 200 DEG C, six district's temperature 200 DEG C, head temperature 190 DEG C, screw speed is 180r/min.
Embodiment 5
Weigh polycaprolactone 90 parts, modified kaolin 5 parts, polycaprolactone grafted maleic anhydride 5 parts, Irganox1010 are 0.9 part, and they are stirred 12 minutes by high-speed mixer, form mixed material；Being put into by aforementioned mixture material in the hopper of double screw extruder, through frit reaction, add modified kaolin at the 3rd place of district by the mode that position, side is reinforced, then extrude, pelletize obtains Modification of kaolin polycaprolactone composite material；Wherein double screw extruder one district temperature 80 DEG C, two district's temperature 170 DEG C, three district's temperature 180 DEG C, four district's temperature 170 DEG C, five district's temperature 180 DEG C, six district's temperature 180 DEG C, head temperature 180 DEG C, screw speed is 120r/min.
Embodiment 6
Weigh polycaprolactone 87 parts, modified kaolin 9 parts, polycaprolactone grafted maleic anhydride 4 parts, Irganox1330 are 1.1 parts, and they are stirred 10 minutes by high-speed mixer, form mixed material；Being put into by aforementioned mixture material in the hopper of double screw extruder, through frit reaction, add modified kaolin at the 3rd place of district by the mode that position, side is reinforced, then extrude, pelletize obtains Modification of kaolin polycaprolactone composite material；Wherein double screw extruder one district temperature 80 DEG C, two district's temperature 170 DEG C, three district's temperature 180 DEG C, four district's temperature 170 DEG C, five district's temperature 180 DEG C, six district's temperature 180 DEG C, head temperature 180 DEG C, screw speed is 160r/min.
Performance test:
Batten test made by the Modification of kaolin polycaprolactone composite material injection machine prepared by above-mentioned enforcement 1-5.In order to embody the superior function of the Modification of kaolin polycaprolactone composite material of the present invention better, by identical method, existing polycaprolactone being made batten simultaneously and carry out performance comparison with the material of the present invention as a comparison case, its result data is in Table 1.
Wherein: hot strength presses ASTMD638 standard testing, elongation at break is pressed ASTMD638 standard testing, bending strength and bending modulus and is pressed ASTMD790 standard testing, and notch impact strength presses ASTMD256 standard testing, and heat distortion temperature presses ASTMD648 standard testing.
The each properties of product test chart of table 1
| Test event | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example |
| Hot strength | MPa | 53 | 51 | 52 | 54 | 56 | 55 | 45 |
| Bending modulus | MPa | 2660 | 2590 | 2445 | 2390 | 2430 | 2550 | 2280 |
| Bending strength | MPa | 69 | 68 | 67 | 60 | 64 | 63 | 50 |
| Notch impact strength | KJ/m2 | 29 | 32 | 31 | 30 | 33 | 31 | 18 |
As can be seen from Table 1, the Modification of kaolin polycaprolactone composite material of the present invention is owing to the addition of modified kaolin and polycaprolactone grafted maleic anhydride (PCL-g-MAH), the impact strength and the curved intensity that make composite are all significantly improved, and are greatly expanded the application of material.Simultaneously, polycaprolactone grafted maleic anhydride (PCL-g-MAH) improves the compatibility of modified kaolin and polycaprolactone, and produce good modified synergic effect between modified kaolin, can react with the still unreacted hydroxyl of kaolin surface this is because PCL-g-MAH molecule one end is polarity anhydride, the PCL-g-MAH molecule other end is similar to the structure of high polymer for flexible interface layer simultaneously, stop kaolinic reunion further, add the compatibility with high polymer.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art's announcement according to the present invention, the improvement made without departing from scope and amendment all should within protection scope of the present invention.
Claims (7)
1. a Modification of kaolin polycaprolactone composite material, it is characterised in that: prepared by weight by following component and make:
Polycaprolactone 80-90 part
Modified kaolin 5-20 part
Polycaprolactone grafted maleic anhydride 3-8 part
Antioxidant 0.1-5 part.
2. a kind of Modification of kaolin polycaprolactone composite material according to claim 1, it is characterised in that: described polycaprolactone is linear polycaprolactone, and its weight average molecular weight is 10000-100000g/mol.
3. a kind of Modification of kaolin polycaprolactone composite material according to claim 1, it is characterised in that: described modified kaolin is made up of for 15-20:5-10:40-50 in mass ratio stearic acid, Cetyltrimethylammonium bromide and Kaolin.
4. a kind of Modification of kaolin polycaprolactone composite material according to claim 1, it is characterised in that: the percent grafting of described polycaprolactone grafted maleic anhydride is 0.3%-2%.
5. a kind of Modification of kaolin polycaprolactone composite material according to claim 1, it is characterized in that: described antioxidant is three (2,4-di-t-butyl) phenyl-phosphite, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, 1,3,5-trimethyl-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) at least one in benzene.
6. the method preparing Modification of kaolin polycaprolactone composite material as claimed in claim 1, it is characterised in that: comprise the following steps:
(1) in mass ratio, stearic acid is added in aqueous solution be made up of Cetyltrimethylammonium bromide and Kaolin, heated and stirred, sucking filtration, washing, dry and to obtain modified kaolin；
(2) weigh dry polycaprolactone, polycaprolactone grafted maleic anhydride and antioxidant by proportioning, and stirred 10～12 minutes by high-speed mixer, form mixed material；
(3) mixed material in (2) is put in the hopper of double screw extruder, through frit reaction, adding, by the mode that position, side is reinforced, the dry modified kaolin prepared through (1) at its 3rd district, the 4th district or the 5th place of district, then extrusion, pelletize obtain Modification of kaolin polycaprolactone composite material.
7. preparation method according to claim 6, it is characterized in that: the screw speed of described double screw extruder is 120～180r/min, each district temperature is district's temperature 70～100 DEG C, two district's temperature 160～190 DEG C, three district's temperature 170～200 DEG C, four district's temperature 160～200 DEG C, five district's temperature 160～200 DEG C, six district's temperature 160～200 DEG C, head temperature 150～190 DEG C.
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| CN107652642A (en) * | 2017-10-23 | 2018-02-02 | 安徽江淮汽车集团股份有限公司 | A kind of polycaprolactone composite material and preparation method thereof |
| CN107629427A (en) * | 2017-10-23 | 2018-01-26 | 安徽江淮汽车集团股份有限公司 | A kind of wear-resisting ageing-resistant polycaprolactone composite material and preparation method thereof |
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| CN102190781A (en) * | 2011-05-11 | 2011-09-21 | 华中师范大学 | Catalytic synthesis process of poly(epsilon-caprolactone) with calcined kaolin as catalyst |
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