CN1775853A - Aliphatic series polyester low-temperature heat-shrinkable pipe composition and its preparing method - Google Patents
Aliphatic series polyester low-temperature heat-shrinkable pipe composition and its preparing method Download PDFInfo
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- CN1775853A CN1775853A CN 200510017296 CN200510017296A CN1775853A CN 1775853 A CN1775853 A CN 1775853A CN 200510017296 CN200510017296 CN 200510017296 CN 200510017296 A CN200510017296 A CN 200510017296A CN 1775853 A CN1775853 A CN 1775853A
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Abstract
The invention relates to a method to make aliphatic series polyester low temperature thermal contraction material combination, which is made up of 100 portions of aliphatic series polyester material, 0.5-1.5 portions of antioxidant and 0.5-3 portions of thermal stabilizer, and 1-0 portions of ethenyl polyfunctional monomer. The thermal contraction temperature of the invention is far lower then that of common thermal contraction material. And it could be used to take the place of the common thermal contraction material and could be biodegrated after using.
Description
Technical field
The present invention relates to aliphatic series polyester low-temperature heat-shrinkable pipe composition and preparation method thereof:
Background technology
The heat-shrinkage material shape-memory material that is otherwise known as, be widely used in each field such as electronics, chemical industry, automobile at present, the base material of preparation heat-shrinkage material mainly is petroleum base resin such as polyethylene, ethylene-vinyl acetate copolymer etc. at present, the main method of making heat-shrinkage material is exactly to produce the intermolecular cross-linking key by the normal temperature cross-linking radiation, again through after the high temperature expansion, by rapid cooling and shaping, the cross-link bond typing that is stretched and is cooled in this process.When this class material is heated again, state before the cross-link bond that stretched can return to and stretch, this has just produced shape memory effect, and this material just is called as material contracting with heat.
But along with the exhausted day by day of disposable fossil resource (as oil, coal) and because the white pollution that a large amount of use caused of petroleum base goods is serious day by day, it is found that to have only utilizes reproducible natural resources production can satisfy the goods of people's needs, and after use, be degraded to carbonic acid gas and water, be only human only way of realizing Sustainable development.Consider that from resource and environment two aspects the Biodegradable polyester material becomes the focus that people pay close attention to gradually just, wherein poly(lactic acid) (PLA) and polypropylene carbonate (PPC) are again this emphasis of wherein being paid close attention to by people.The prerequisite of producing heat-shrinkage material produces the intermolecular cross-linking key in the matrix of material, because PLA and PPC itself are radiation cleavage type macromolecular materials, therefore how to realize that their radiation crosslinking is one of research direction of people always.The people such as F.Yoshii of the high rugged institute of Japan in 2005 point out on polymkeric substance [Polymer 46 (2005) 4695-4703] magazine, triallyl isocyanurate is a kind of efficient hardening linking agent of PLA, people such as M.Suhartini is at applied polymer science (J.Appl.polym.scij88 before this, 2238-2246,2003) publish an article and point out, strengthen thermostability and temperature classification that radiation crosslinking can effectively improve another kind of aliphatic polyester (poly butylene succinate), particularly when probe temperature is higher than the fusing point (113 ℃) of poly butylene succinate, the physical strength of non-crosslinked material completely loses, and just occurs this phenomenon during cross-linked material to 220 ℃.And in this research, triallyl isocyanurate is the most effective reinforcement linking agent equally.Similar result also appears at people such as G.M.Zhu and is published in the article of using polymerization magazine (J.Appl.polym.scij95 634-639,2005).But yet there are no the report of strengthening crosslinked result about PPC so far.
Summary of the invention
Purpose of the present invention is exactly to utilize PLA and PPC to strengthen on the basis of radiation crosslinking, developing a kind of brand-new aliphatic series polyester low-temperature heat-shrinkable pipe.The heat shrink temperature of this tubing is far below the shrinkage temperature of general heat-shrinkage material, it not only can be used for substituting general heat-shrinkable pipe, and (require the shrinkage temperature of thermal shrinkage pipe material to be lower than 45 ℃ this moment, in order to avoid injury human tissue cell) has great application prospect in the human tissue engineering reconstructive operation.
It is as follows that raw material of the present invention is formed weight ratio: aliphatic poly ester material: 100; Oxidation inhibitor: 0.5-1.5; Thermo-stabilizer: 0.5-3; Vinyl polyfunctional monomer: 1-10;
Wherein said aliphatic poly ester material is poly(lactic acid), polypropylene carbonic ether or both mixtures, and both blend weight ratios (poly(lactic acid): polypropylene carbonate) 10: 90-90: between 10;
Wherein said oxidation inhibitor is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid;
Wherein said thermo-stabilizer is an epoxy soybean oil;
Wherein said vinyl polyfunctional monomer is a triallyl isocyanurate;
The effect of described oxidation inhibitor and thermo-stabilizer is to guarantee that polyester material can not produce thermal destruction in hot procedure, and its consumption can not exert an influence to next step radiation crosslinking again simultaneously; The effect of vinyl polyfunctional monomer is the room temperature radiation crosslinking that promotes polyester material, improves its gel content.It is generally acknowledged that the vinyl polyfunctional monomer promotes that the crosslinked mechanism of action was divided into for two steps, the first step is the graft reaction that the vinyl polyfunctional monomer takes place on the free polymer readical that irradiation causes, second step was to react the generation cross-link bond between two keys remaining between the polyfunctional monomer that connects.In the irradiation process, the freeradical yield of polymkeric substance can not increase owing to the adding of polyfunctional monomer, therefore the effect of polyfunctional monomer just can not be carried out crosslinking reaction with those and make its resurrection from disappearing from the free radical graft reaction that goes out, and it is just passable to add a spot of polyfunctional monomer; The aliphatic poly ester material is poly(lactic acid), polypropylene carbonate or both mixtures, use the purpose of mixture to be to utilize the good processing characteristics of poly(lactic acid) on the one hand, improve the extrusioning shaping and the expander processing stability of thermal shrinkage pipe material, adjust the shrinkage temperature of thermal shrinkage pipe material on the other hand with polypropylene carbonate.
The preparation method of aliphatic series polyester low-temperature heat-shrinkable pipe composition of the present invention, undertaken by following step and condition: will put into homogenizer by the load weighted various raw materials of proportioning and mix 5 minutes, to heat length-to-diameter ratio be to melt extrude granulation in 36: 1 the parallel dual-screw extruding machine with having 8 districts for the material that mixes, the masterbatch of making was dried in vacuum drying oven 48 hours, use Φ 25 single screw extrusion machine extruding pipe materials then, squeeze good tubing and send into irradiation 1-10Mrad in Co-60 source or the rumbatron, subsequently with malleation pipe-expanding machine expander make can thermal contraction between 30--60 ℃ tubing;
The hot-work interval of wherein said masterbatch and tubing is between 50--190 ℃;
The dosage of wherein said irradiation is between the 3-7Mrad at 1-10Mrad and best dosage interval;
The heat shrink temperature of aliphatic series polyester low-temperature heat-shrinkable pipe composition of the present invention is far below the shrinkage temperature of general heat-shrinkage material, its shrinkage temperature interval between 30--60 ℃, the maximum collapse multiplying power radially 0.5-1.5 doubly, the axial shrinkage multiplying power be 1-3 doubly.It not only can be used for substituting general heat-shrinkable pipe, and (require the shrinkage temperature of thermal shrinkage pipe material to be lower than 45 ℃ this moment in the human tissue engineering reconstructive operation, in order to avoid injury human tissue cell) have great application prospect, and can biological degradation after use.
Embodiment
Embodiment 1-6:
Take by weighing molecular weight and be 80,000 polypropylene carbonate (production of Meng Xi group) 5000 grams; oxidation inhibitor is β-(4-hydroxyl-3; the 5-di-tert-butyl-phenyl) positive octadecyl ester 50 grams of propionic acid; epoxy soybean oil 100 grams; its weight of triallyl isocyanurate is respectively 50; 100; 150; 200; 300 and 500 grams; put into 10 kilograms high and stir machine stirring 5 minutes; add dual-screw-stem machine (Haake then with the heating of 8 districts; PTW--24) Heating temperature in 8 districts is respectively 100 in; 120; 130; 150; 165; 160; 150; 150 ℃; the material bar of extruding is used the dicing machine granulation after the cold water cooling; the masterbatch of making places vacuum drying oven oven dry 48 hours; single screw rod is extruded into tubing, and (single screw rod is Haake-252P; four district's Heating temperatures are 100; 130; 150; 140 ℃; head temperature is 135 ℃) pipe diameter is 2mm; measuring length respectively is 5 sections of 0.5 mitron materials; put into thickness and be 30 microns PE bag; charge into the N2 protection; be placed on irradiation 1Mrad in 7.5 ten thousand Curie's cobalt-60 irradiation source; 3Mrad; 5Mrad; 7Mrad and 10Mrad; taking by weighing 0.3 gram left and right sides tubing behind the irradiation wraps with nickel screen; put into Soxhlet extractor; the weight of residuum was calculated in the chloroform extracting in 24 hours; calculated for gel content the results are shown in Table one.As seen working as TAIC content by table one result surpasses after 4%, the gel content of PPC irradiation system will effectively be improved, particularly when TAIC content when irradiation dose is between 3--7Mrad greater than 6%, the gel content of its tubing helps making various heat-shrinkable pipes.
Table 1: under the different irradiation doses, the PPC gel content is with the variation of polyfunctional monomer content
Embodiment 7:
Get as 30 meters of the tubing as described in the embodiment 6, with malleation pipe-expanding machine expander, wherein heating bath is 50 ℃ of hot water with 1.5Mev dynamitron irradiation 7Mrad tubing, and air pressure is a 0.5MPa Vacuum shaping and with 18--25 ℃ of cold water cooling.Vacuum shaping part internal diameter is 5mm, and the tubing pulling speed is 2 meters/minute, and the traction multiplying power is 1.5, and the tubing after the expansion has good shape memory, and its degree of heat-shrinkage is 30 ℃.
Embodiment 8: taking by weighing weight-average molecular weight is 180,000 poly(lactic acid) (D type lactic acid content is 7%) (the positive group in sea, Zhejiang produces), 5000 grams, oxidation inhibitor 3.5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid 75 grams, 150 gram epoxy soybean oils and 250 gram triallyl isocyanurate height are mixed and are closed, use Haake PTW-24 double-screw extruding pelletizing, 8 district's Heating temperatures are respectively 130,150,165,175,185,175,170,160 ℃, oven dry is 48 hours in 50 ℃ of vacuum drying ovens of the pellet of making, and is respectively 145 with the heating of four districts, 175,185,170, head temperature is that the single screw rod of 165 ℃ Haake-252P is extruded the PLA tubing that internal diameter is 1mm.Squeeze good tubing 1.5MeV dynamitron irradiation 6.5Mard, be 3mm with malleation pipe-expanding machine expander to internal diameter then, wherein the heated water bath temperature is 90 ℃, air pressure is 0.5MPa, tubing pulling speed position rice/minute, the traction multiplying power is 1, and expansion its heat shrink temperature of tubing after the meeting is 60 ℃.
Embodiment 9-13:
Raw material and complete processing are with embodiment 8, wherein oxidation inhibitor 3.5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid 25 restrains, it is 1Mrad, 3Mrad, 5Mrad, 7Mran and 10Mrad that vinyl polyfunctional group content is respectively 100 grams, 150 grams, 200 grams, 300 grams and 500 gram irradiation doses, and the expansivity of tubing sees Table 2:
Table 2: crosslinked PLA tubing spreading performance
X: can't expand O: discontinuous expansion V: can expand continuously
Embodiment 14-22:
The course of processing such as embodiment 8, take by weighing polypropylene carbonate and poly-lactic acid mixture 5000 grams, wherein the weight percentage of poly(lactic acid) is respectively 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90%, oxidation inhibitor 3.5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid 60 grams, thermo-stabilizer 25 grams, vinyl polyfunctional monomer 250 grams, when poly(lactic acid) content≤40%, prilling temperature is 90,110,130,150,175,170,165,165 ℃, the pellet of preparation is dry in being lower than 40 ℃ vacuum drying oven, behind the irradiation 6.5Mrad, in heated water bath is expander in 70 ℃ the malleation pipe-expanding machine, and prepared tubing heat shrink temperature and multiplying power see Table 2; Prilling temperature is 110,130,150,170,185,175,170,160 ℃ when poly(lactic acid) content 〉=50%, pellet in being lower than 60 ℃ vacuum drying oven dry 48 hours, behind the irradiation 6.5Mrad, in heated water bath is expander in 90 ℃ the malleation pipe-expanding machine, and prepared aliphatics low temperature thermal contraction heat shrink temperature and multiplying power see Table 3:
Table 3:PPC/PLA blend heat-shrinkable pipe shrinkage temperature and multiplying power
| Embodiment | PC/PL A | Heat shrink temperature (℃) | The maximum multiplying power of vertically shrinking | Maximum axial is shunk multiplying power |
| 14 | 90∶10 | 32 | 1.0 | 1.0 |
| 15 | 80∶20 | 36 | 1.0 | 1.5 |
| 16 | 70∶30 | 37 | 1.2 | 1.5 |
| 17 | 60∶40 | 45 | 1.2 | 1.5 |
| 18 | 50∶50 | 50 | 1.2 | 1.5 |
| 19 | 40∶60 | 51 | 1.2 | 2.0 |
| 20 | 30∶70 | 53 | 1.5 | 2.0 |
| 21 | 20∶80 | 55 | 1.5 | 2.7 |
| 22 | 10∶90 | 58 | 1.5 | 2.7 |
Embodiment 23-27:
Raw material and complete processing such as embodiment 17, oxidation inhibitor β-(4-hydroxyl-3 wherein, the 5-di-tert-butyl-phenyl) positive octadecyl ester 30 grams of propionic acid, thermo-stabilizer 75 grams, vinyl polyfunctional monomer content is respectively 100 grams, 150 grams, 200 grams, 300 grams and 500 grams, after irradiation dose is 1Mrad, 3Mrad, 5Mrad, 7Mran and 10Mrad, the thermal enlargement such as the table 4 of tubing:
Table 4: heat shrink temperature is 45 ℃ blend expanding thermal shrinkage tube performance
X: can't expand O: discontinuous expansion V: can expand continuously
Embodiment 28-32:
Raw material and complete processing such as embodiment 16, oxidation inhibitor β-(4-hydroxyl-3 wherein, the 5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid is 70 grams, thermo-stabilizer is 120 grams, vinyl polyfunctional monomer content is respectively 100 grams, 150 grams, 200 grams, 300 grams and 500 grams, irradiation dose is 1Mrad, 3Mrad, 5Mrad, 7Mran and 10Mrad, the thermal enlargement such as the table 5 of tubing:
Table 5: heat shrink temperature is at 37 ℃ blend expanding thermal shrinkage tube
X: can't expand O: discontinuous expansion V: can expand continuously
Claims (7)
1. an aliphatic series polyester low-temperature heat-shrinkable pipe composition is characterized in that, it is as follows that its raw material is formed weight ratio: aliphatic poly ester material: 100 oxidation inhibitor: 0.5-1.5; Thermo-stabilizer: 0.5-3; Vinyl polyfunctional monomer: 1-10.
2. aliphatic series polyester low-temperature heat-shrinkable pipe composition as claimed in claim 1, it is characterized in that, described aliphatic poly ester material is poly(lactic acid), polypropylene carbonate or both mixtures, and both blend weight ratios (poly(lactic acid): polypropylene carbonate) 10: 90-90: between 10.
3. aliphatic series polyester low-temperature heat-shrinkable pipe composition as claimed in claim 1 or 2 is characterized in that described oxidation inhibitor is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid.
4. as the described aliphatic series polyester low-temperature heat-shrinkable pipe composition of 1,2 or 3 any one claim, it is characterized in that described thermo-stabilizer is an epoxy soybean oil.
5. as the described aliphatic series polyester low-temperature heat-shrinkable pipe composition of 1,2,3 or 4 any one claim, it is characterized in that described vinyl polyfunctional monomer is triallyl isocyanurate (TAIC).
6. the preparation method of aliphatic series polyester low-temperature heat-shrinkable pipe composition as claimed in claim 1, it is characterized in that being undertaken by following step and condition: will be in proportion load weighted various raw material put into homogenizer and mix, the material that mixes melt extrudes granulation with parallel dual-screw extruding machine, the masterbatch of making is dried in vacuum drying oven, use the single screw extrusion machine extruding pipe material then, squeeze good tubing and send into irradiation 1-10Mrad in Co-60 source or the rumbatron, make heat-shrinkable pipe with malleation pipe-expanding machine expander subsequently.
7. the preparation method of aliphatic series polyester low-temperature heat-shrinkable pipe composition as claimed in claim 6, it is characterized in that being undertaken by following step and condition: load weighted various raw material is put into homogenizer mixing 5 minutes in proportion, to heat length-to-diameter ratio be to melt extrude granulation in 36: 1 the parallel dual-screw extruding machine with having 8 districts for the material that mixes, the masterbatch of making was dried in vacuum drying oven 48 hours, use Φ 25 single screw extrusion machine extruding pipe materials then, squeeze good tubing and send into irradiation 1-10Mrad in Co-60 source or the rumbatron, make heat-shrinkable pipe with malleation pipe-expanding machine expander subsequently; The hot-work interval of described masterbatch and tubing is between 50--190 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532454C (en) * | 2007-04-02 | 2009-08-26 | 中国科学院长春应用化学研究所 | Heat resistant polylactic acid-base composite material and its preparation process |
| CN103625061A (en) * | 2013-11-29 | 2014-03-12 | 卫辉市银金达薄膜有限公司 | Tape-casting environment-friendly degradable heat-shrink film and manufacturing method thereof |
| CN111978695A (en) * | 2020-08-14 | 2020-11-24 | 郑州大学 | Degradable full-bio-based high-toughness polylactic acid composite material and preparation method thereof |
| CN113789039A (en) * | 2021-09-29 | 2021-12-14 | 江苏景宏新材料科技有限公司 | Biodegradable polyester heat shrinkable film and preparation method thereof |
| CN114456563A (en) * | 2022-03-16 | 2022-05-10 | 贵州省材料产业技术研究院 | PLA-based heat shrinkable film and preparation method thereof |
| CN115746524A (en) * | 2022-11-24 | 2023-03-07 | 扬州惠通新材料有限公司 | Preparation method of biodegradable micro-foaming polylactic acid material |
-
2005
- 2005-11-21 CN CN 200510017296 patent/CN1775853A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532454C (en) * | 2007-04-02 | 2009-08-26 | 中国科学院长春应用化学研究所 | Heat resistant polylactic acid-base composite material and its preparation process |
| CN103625061A (en) * | 2013-11-29 | 2014-03-12 | 卫辉市银金达薄膜有限公司 | Tape-casting environment-friendly degradable heat-shrink film and manufacturing method thereof |
| CN103625061B (en) * | 2013-11-29 | 2016-06-08 | 卫辉市银金达薄膜有限公司 | The environment-friendly type degradable heat-shrinkable film of a kind of curtain coating machine-shaping and manufacture method thereof |
| CN111978695A (en) * | 2020-08-14 | 2020-11-24 | 郑州大学 | Degradable full-bio-based high-toughness polylactic acid composite material and preparation method thereof |
| CN111978695B (en) * | 2020-08-14 | 2023-02-28 | 郑州大学 | Degradable full-bio-based high-toughness polylactic acid composite material and preparation method thereof |
| CN113789039A (en) * | 2021-09-29 | 2021-12-14 | 江苏景宏新材料科技有限公司 | Biodegradable polyester heat shrinkable film and preparation method thereof |
| CN114456563A (en) * | 2022-03-16 | 2022-05-10 | 贵州省材料产业技术研究院 | PLA-based heat shrinkable film and preparation method thereof |
| CN115746524A (en) * | 2022-11-24 | 2023-03-07 | 扬州惠通新材料有限公司 | Preparation method of biodegradable micro-foaming polylactic acid material |
| CN115746524B (en) * | 2022-11-24 | 2023-12-19 | 扬州惠通新材料有限公司 | Preparation method of biodegradable micro-foaming polylactic acid material |
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