CN104479315A - Inorganic filler full-biodegradable composite as well as preparation method and application of inorganic filler full-biodegradable composite - Google Patents
Inorganic filler full-biodegradable composite as well as preparation method and application of inorganic filler full-biodegradable composite Download PDFInfo
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- CN104479315A CN104479315A CN201410748500.3A CN201410748500A CN104479315A CN 104479315 A CN104479315 A CN 104479315A CN 201410748500 A CN201410748500 A CN 201410748500A CN 104479315 A CN104479315 A CN 104479315A
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Abstract
The invention discloses an inorganic filler full-biodegradable composite as well as a preparation method and application of the inorganic filler full-biodegradable composite. The inorganic filler full-biodegradable composite comprises the following components: 5-50 parts of inorganic filler full-biodegradable masterbatches and 50-95 parts of polylactic acid, wherein the inorganic filler full-biodegradable masterbatches comprise the following components: 20-80 parts of polylactic acid, 20-80 parts of inorganic filler, 0.1-10 parts of a lubricating agent and 0.1-5 parts of a compatilizer; and the inorganic filler is one or a combination of modified kaolin, modified white carbon black and modified montmorillonite. According to the inorganic filler full-biodegradable composite, the modified montmorillonite, the modified kaolin or the modified white carbon black is added as an enhancer, and an epoxy acrylic copolymer is introduced as the compatilizer, so that the compatibility of the inorganic filler and matrix resin is enhanced, and the uniform dispersion is achieved; and the masterbatches are added into the polylactic acid, so that the problem of relatively low tearing strength of a polylactic acid film and a sheet can be effectively improved.
Description
Technical field
The present invention relates to field of high polymer material modification, be specifically related to a kind of mineral filler biodegradable composite material and its preparation method and application.
Background technology
Poly(lactic acid) (PLA) is a kind of is raw material with cereal starch, obtains lactic acid, then through polyreaction, finally obtain polylactic resin through biological fermentation.It has two large advantages: the first, biodegradable, is easily decomposed into carbon monoxide and water, can be absorbed by plants, recycle in soil.The second, be non-petroleum base plastics, derive from the renewable resourcess such as plant, under the situation that petroleum-based energy day is becoming tight, development research polylactic resin seems particularly important.The performance of poly(lactic acid) itself is similar to general-purpose plastics polypropylene, as high in modulus, tensile strength is large and processability good.But this type of material exists breach when using as film or sheet material extends low shortcoming, and the tear-resistant poor performance of its film or sheet material, has had a strong impact on use properties.
Also there is at present various poly(lactic acid) and the mixing biodegradable material of conventional plastic on the market, but the conventional plastic composition of many deals need be added owing to improving its toughness, therefore can not accomplish degradable, in fact, have and much only belong to apparent disintegration and not biological degradation truly.As CN201010205306.2 discloses a kind of high-toughness polylactic acid resin, MBS selected by its toughner, citric acid ester type selected by softening agent, although promote comparatively obvious for the notched Izod impact strength of poly(lactic acid) and elongation at break, but both is non-degradable composition, do not reach the requirement of complete biodegradable, the improvement for film material or sheet material tear strength is also not mentioned.CN201310041457.2 discloses a kind of full-biodegradable polylactic acid matrix material, by high molecular and the composite use of low molecular weight, the toughness of material can be improved, but it is lower still to there is tear strength in modified film material or sheet material, consistency is poor, and use procedure is easier to occur problems of crack.
Therefore, how to improve lactic acid film material or sheet material tear strength and don't affect its biodegradability be expand poly(lactic acid) apply the problem that must solve.
Summary of the invention
Primary and foremost purpose of the present invention is the deficiency overcoming above-mentioned existing polylactic acid membrane material and sheet material existence, provides the mineral filler biodegradable composite material that a kind of consistency is good, can improve matrix resin tear strength.
Another object of the present invention is to the preparation method that above-mentioned mineral filler biodegradable composite material is provided.
The present invention is achieved through the following technical solutions:
A kind of mineral filler biodegradable composite material, comprises the component of following weight part:
Mineral filler complete biodegradable master batch 5 ~ 50 parts
Poly(lactic acid) 50 ~ 95 parts
Wherein, described mineral filler complete biodegradable master batch, comprises the component of following weight part:
Poly(lactic acid) 20 ~ 80 parts
Mineral filler 20 ~ 80 parts
Lubricant 0.1 ~ 10 part
Compatilizer 0.1 ~ 5 part
Wherein, described mineral filler is one in modified kaolin, modified white carbon black or modified montmorillonoid or its combination.
Described modified montmorillonoid is through alkyl quaternary ammonium salts surface modification, and particle size range is 300 order ~ 800 orders;
Described modified kaolin is through silane coupling agent surface modification, and particle size range is 4 ~ 20 microns;
Described modified white carbon black is through silane coupling agent surface modification, and particle size range is 20 ~ 60 nanometers.
Described silane coupling agent can be one or more in aminopropyl triethoxysilane (KH550), glycidyl ester oxy propyl trimethoxysilane (KH560), methacryloxypropyl trimethoxy silane (KH570).
The consumption of described silane coupling agent is 0.1 ~ 20% of mineral filler quality.
Described alkyl quaternary ammonium salts can be cetyltrimethyl ammonium salt, octadecyltrimethylammonium salt, cetyldimethylbenzylammonium salt, octadecyl dimethyl benzyl ammonium salt, hexadecyldimethyl benzyl ammonium iso-octyl ammonium salt, octadecyldimethyl iso-octyl ammonium salt, hexadecyldimethyl benzyl ammonium propenyl ammonium salt, octadecyldimethyl propenyl ammonium salt, hexadecyldimethyl benzyl ammonium hydroxyethyl ammonium salt, octadecyldimethyl hydroxyethyl ammonium salt, two dodecyl dimethyl ammonium salt, two octadecyldimethyl ammonium salt, one or more in the two octadecyl methyl benzyl ammonium salt of di-cetyl dimethyl ammonium salt or double hexadecyl methylbenzylammonium salt.
The consumption of described alkyl quaternary ammonium salts is 0.1 ~ 60% of mineral filler quality.
The weight-average molecular weight > 70000 of described poly(lactic acid).
Described lubricant is the mixture of one or more in stearic acid and salt, montanin wax, erucicamide, amine hydroxybenzene or ethylene bis stearamide.
Described compatilizer is epoxy types, mixed by one or more epoxies acrylic copolymer and form, be preferably in structure containing 2 ~ 15 epoxide groups, molar mass is the epoxies acrylic copolymer of 1000 ~ 7000g/mol, such compatilizer can with the end group of selected poly(lactic acid), as hydroxyl or carboxyl reaction, reach the object expanding straight or branched and increase consistency, improve the dispersiveness of mineral filler and the mechanical property of composition.
The preparation of mineral filler biodegradable composite material of the present invention, comprises the following steps:
(1) first poly(lactic acid) is dried 3 ~ 10 hours at 80 DEG C;
(2) dried poly(lactic acid) 20-80 part and mineral filler 20-80 part, lubricant 0.1-10 part, compatilizer 0.1-5 part are carried out mechanical blending 3 ~ 10 minutes in high mixer;
(3) carry out fusion plastification, extrude in material feeding twin screw extruder step (2) mixed, namely granulation obtain mineral filler complete biodegradable master batch;
(4) mineral filler complete biodegradable master batch 5-50 part step (3) obtained mixes 3 ~ 10 minutes with poly(lactic acid) 50-95 part normal temperature in high mixer, then joins in dual-screw-stem machine and extrudes blended granulation, obtain mineral filler biodegradable composite material.
Mineral filler biodegradable composite material of the present invention is as the application in film material or sheet material.
The present invention compared with prior art, has following beneficial effect:
(1) mineral filler complete biodegradable master batch of the present invention is using poly(lactic acid) as the matrix of mineral filler, has considered the degradable performance of matrix material and the consistency of matrix;
(2) mineral filler complete biodegradable master batch of the present invention is by adding modified montmorillonoid, modified kaolin or modified white carbon black as toughener, add the consistency of mineral filler and matrix resin, be uniformly dispersed, this master batch is added in poly(lactic acid), under the prerequisite not affecting its biodegradability, effectively can improve copolyester film and the lower problem of sheet material tear strength;
(3) the present invention by introducing epoxies acrylic copolymer as compatilizer in above-mentioned master batch, further improves the consistency of modified inorganic filler and poly(lactic acid), improve the tear strength of intermingling material.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Raw material of the present invention is as follows:
Modified kaolin: KH560 modified kaolin, particle size range is 4 ~ 20 microns;
Modified white carbon black: KH550 modified white carbon black, particle size range is 20 ~ 60 nanometers;
Modified montmorillonoid: cetyltrimethyl ammonium salt modified montmorillonoid, particle size range is 300 order ~ 700 orders;
The detection method that the present invention is used or standard are:
Mensuration the 3rd part of tensile strength: GB/T 1040.3 plastic tensile performance: the test conditions of film and thin slice;
Mensuration the 3rd part of elongation at break: GB/T 1040.3 plastic tensile performance: the test conditions of film and thin slice;
The mensuration part 2 of resistance to tearing: GB/T 16578.2 plastics film and the tear-resistant performance of thin slice: Ai Laimenduofufa.
the preparation of mineral filler complete biodegradable master batch:
By the proportioning of table 1, first by poly(lactic acid) in an oven 80 DEG C dry 5 hours; By dried poly(lactic acid) and mineral filler, profit
Lubrication prescription, compatilizer carry out mechanical blending 5 minutes in high mixer; Carry out fusion plastification in material feeding twin screw extruder step (2) mixed, extrude, namely granulation obtains A1 ~ A5, B1-B5 mineral filler complete biodegradable master batch;
Described twin screw extruder is equidirectional parallel double-screw extruder, and its design temperature is: a district: 60 ~ 90 DEG C, 2nd district: 120 ~ 150 DEG C, 3rd district: 140 ~ 170 DEG C, 4th district: 170 ~ 190 DEG C, 5th district: 170 ~ 190 DEG C, 6th district: 170 ~ 190 DEG C,
7th district: 170 ~ 190 DEG C, 8th district: 170 ~ 190 DEG C, 9th district: 170 ~ 190 DEG C, head: 170-190 DEG C, screw speed: 300rpm.Screw slenderness ratio is 40:1.
Table 1 A 1 ~ A5, B1-B5 mineral filler complete biodegradable master batch (weight part)
embodiment 1-5 and comparative example 1-5
By mineral filler complete biodegradable master batch obtained above with poly(lactic acid) in table 2 ratio normal temperature mixing 5min in high mixer, then join in dual-screw-stem machine and extrude blended granulation, obtain mineral filler biodegradable composite material.By matrix material as extruding in inflation film manufacturing machine, arranging extruder temperature is 140 ~ 180 DEG C, and extrusion-blown modling becomes thickness to be 25 micron films, and thin film mechanical performance is as table 2.
Table 2 embodiment and each component of comparative example form and results of property
As can be seen from the contrast of comparative example 1 and embodiment 3, adding of lubricant can effectively prevent the reunion of filler and make filler have higher dispersing property, and blended rear obtained film product has higher mechanical property particularly tear strength.As can be seen from the contrast of comparative example 2 and embodiment 3, adding of epoxies acrylic copolymer can improve the consistency of mineral filler and base material and the tear strength of composition.As can be seen from the contrast of comparative example 3-5 and embodiment 3, polynite gets a promotion with the consistency of poly(lactic acid) after surface modification treatment, modified montmorillonoid is compared with calcium carbonate with unmodified polynite, talcum powder, better consistency is had with poly(lactic acid), obtained matrix material not only can reduce costs, and effectively can improve polylactic acid film and the lower problem of sheet material tear strength.
Claims (8)
1. a mineral filler biodegradable composite material, is characterized in that, comprises the component of following weight part:
Mineral filler complete biodegradable master batch 5 ~ 50 parts
Poly(lactic acid) 50 ~ 95 parts
Described mineral filler complete biodegradable master batch, comprises the component of following weight part:
Poly(lactic acid) 20 ~ 80 parts
Mineral filler 20 ~ 80 parts
Lubricant 0.1 ~ 10 part
Compatilizer 0.1 ~ 5 part
Wherein, described mineral filler is one in modified kaolin, modified white carbon black or modified montmorillonoid or its combination.
2. mineral filler biodegradable composite material according to claim 1, is characterized in that: described modified montmorillonoid is that particle size range is 300 order ~ 800 orders through alkyl quaternary ammonium salts surface modification; Described modified kaolin is through silane coupling agent surface modification, and particle size range is 4 ~ 20 microns; Described modified white carbon black is through silane coupling agent surface modification, and particle size range is 20 ~ 60 nanometers.
3. mineral filler biodegradable composite material according to claim 1, is characterized in that: the weight-average molecular weight > 70000 of described poly(lactic acid).
4. mineral filler biodegradable composite material according to claim 1, is characterized in that: described lubricant is the mixture of one or more in stearic acid and salt, montanin wax, erucicamide, amine hydroxybenzene or ethylene bis stearamide.
5. mineral filler biodegradable composite material according to claim 1, is characterized in that: described compatilizer is epoxy types, is mixed form by one or more epoxies acrylic copolymer.
6. mineral filler biodegradable composite material according to claim 5, is characterized in that: described compatilizer is that molar mass is the epoxies acrylic copolymer of 1000 ~ 7000g/mol containing 2-15 epoxide group in structure.
7. the preparation method of the mineral filler biodegradable composite material described in any one of claim 1 ~ 6, is characterized in that: comprise the following steps:
(1) first poly(lactic acid) is dried 3 ~ 10 hours at 80 DEG C;
(2) dried poly(lactic acid) 20-80 part and mineral filler 20-80 part, lubricant 0.1-10 part, compatilizer 0.1-5 part are carried out mechanical blending 3 ~ 10 minutes in high mixer;
(3) carry out fusion plastification, extrude in material feeding twin screw extruder step (2) mixed, namely granulation obtain mineral filler complete biodegradable master batch;
(4) mineral filler complete biodegradable master batch 5-50 part step (3) obtained mixes 3 ~ 10 minutes with poly(lactic acid) 50-95 part normal temperature in high mixer, then joins in dual-screw-stem machine and extrudes blended granulation, obtain mineral filler biodegradable composite material.
8. the mineral filler biodegradable composite material described in any one of claim 1 ~ 6 is as the application in film material or sheet material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947116A (en) * | 2017-04-26 | 2017-07-14 | 苏州汉丰新材料股份有限公司 | Full biological poly lactic acid flexible packing material and preparation method thereof |
| CN108164942A (en) * | 2017-11-30 | 2018-06-15 | 芜湖林电子科技有限公司 | It is a kind of for PLA composite materials of 3D printing and preparation method thereof |
| CN108587096A (en) * | 2018-05-15 | 2018-09-28 | 战国昌 | A kind of environmentally protective soil matrix material and its preparation process |
| CN109266233A (en) * | 2018-08-08 | 2019-01-25 | 北京众邦健业印刷有限责任公司 | Tape substrate, adhesive tape and preparation method with it |
| CN111534066A (en) * | 2020-05-13 | 2020-08-14 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
| CN112375354A (en) * | 2020-11-17 | 2021-02-19 | 杨勇 | Carbon fiber polylactic acid filling master batch and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059342A (en) * | 2013-03-19 | 2014-09-24 | 上海杰事杰新材料(集团)股份有限公司 | Inorganic-filling material full-biodegradation composite material with high compatibility and preparation method thereof |
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2014
- 2014-12-10 CN CN201410748500.3A patent/CN104479315A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059342A (en) * | 2013-03-19 | 2014-09-24 | 上海杰事杰新材料(集团)股份有限公司 | Inorganic-filling material full-biodegradation composite material with high compatibility and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947116A (en) * | 2017-04-26 | 2017-07-14 | 苏州汉丰新材料股份有限公司 | Full biological poly lactic acid flexible packing material and preparation method thereof |
| CN106947116B (en) * | 2017-04-26 | 2019-11-08 | 苏州汉丰新材料股份有限公司 | Full biological poly lactic acid flexible packing material and preparation method thereof |
| CN108164942A (en) * | 2017-11-30 | 2018-06-15 | 芜湖林电子科技有限公司 | It is a kind of for PLA composite materials of 3D printing and preparation method thereof |
| CN108587096A (en) * | 2018-05-15 | 2018-09-28 | 战国昌 | A kind of environmentally protective soil matrix material and its preparation process |
| CN109266233A (en) * | 2018-08-08 | 2019-01-25 | 北京众邦健业印刷有限责任公司 | Tape substrate, adhesive tape and preparation method with it |
| CN109266233B (en) * | 2018-08-08 | 2021-02-19 | 北京众邦健业印刷有限责任公司 | Adhesive tape base material, adhesive tape with same and preparation method |
| CN111534066A (en) * | 2020-05-13 | 2020-08-14 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
| CN111534066B (en) * | 2020-05-13 | 2022-07-05 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
| CN112375354A (en) * | 2020-11-17 | 2021-02-19 | 杨勇 | Carbon fiber polylactic acid filling master batch and preparation method thereof |
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Application publication date: 20150401 |