CN104817807A - Environment-friendly recyclable cross-linked TPE (thermoplastic elastomer) tourniquet and preparation method thereof - Google Patents
Environment-friendly recyclable cross-linked TPE (thermoplastic elastomer) tourniquet and preparation method thereof Download PDFInfo
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- CN104817807A CN104817807A CN201510191721.XA CN201510191721A CN104817807A CN 104817807 A CN104817807 A CN 104817807A CN 201510191721 A CN201510191721 A CN 201510191721A CN 104817807 A CN104817807 A CN 104817807A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention discloses an environment-friendly recyclable cross-linked TPE (thermoplastic elastomer) tourniquet which is made of raw materials including SEBS (styrene-ethylene-butylene-styrene), MAH-g-SEBS, PP (polypropylene), MAH-g-PP, carboxylation chitosan and white oil. The invention further discloses a method for preparing the environment-friendly recyclable cross-linked TPE tourniquet under the condition of vacuum injection molding and recycling the tourniquet under ultraviolet light.
Description
Technical field
The present invention relates to field of medical materials, more specifically, the present invention relates to recyclable crosslinked TPE tourniquet of a kind of environment-friendly type and preparation method thereof.
Background technology
Thermoplastic elastomer TPE (Thermoplastic Elastomer) is a kind of snappiness, high strength, high resilience with rubber, and having again can the material of injection molding feature.There is environment-protecting asepsis safety, durometer level is wide, has excellent tint permanence, soft-touch, weathering resistance, fatigue resistance and temperature tolerance, processing characteristics is superior, need not sulfuration, can recycle and reduce costs, both can secondary injection molding, with body material coating and bondings such as PP, PE, PC, PS, ABS, also can be shaping separately.
Thermoplastic elastomer TPE tourniquet is as a kind of Novel environment-friendlymaterial material, and alternative former tube for blood transfusion,latex, plays the effect temporarily suppressing blood flow, tube for blood transfusion,latex than original substitute has cheap, easy to carry, use the advantage of health, there are market outlook widely.Medical TPE tourniquet is generally that raw material prepares with thermoplastics polypropylene (PP), thermoplastic elastomer hydrogenated styrene-butadiene-styrene block copolymers (SEBS) and suitable filler.Wherein, SEBS has excellent caoutchouc elasticity, excellent weathering resistance, lower temperature resistance, environmental-protecting performance etc., is suitable for very much preparing medical tourniquet, but also there is the shortcomings such as rigidity is excessive, compression set is large, density is high.Use PP modified SEBS, SEBS melt viscosity can be reduced on the one hand, make SEBS be easy to processing; Effectively can improve the mechanical property of SEBS elastomer system on the other hand.In addition, PP is cheap, can reduce the cost of SEBS elastomer material.Filler being applied in the polymer can be improved the mechanical property of material and thermomechanical property to a certain extent, meanwhile, filler add the cost also greatly reducing material, change more economical, practical.
In prior art, in order to obtain more high performance TPE medical tourniquet, usually need to carry out crosslinking Treatment to TPE, to improve its mechanical strength and screen resilience.Although crosslinking Treatment is very effective, because tourniquet is disposable products, the TPE processability after crosslinked is poor, is difficult to recycle, is unfavorable for environmental protection.
Therefore, be starved of by formula and the improvement of production technique, to obtain, both there is higher degree of crosslinking and intensity, there is again the medical TPE tourniquet of good recyclable, cycling processability.
Summary of the invention
In order to solve the problem, one aspect of the present invention provides environment-friendly type recyclable crosslinked TPE tourniquet, is prepared from by the raw material comprising following weight part:
In one embodiment, in described MAH-g-SEBS, the percentage of grafting of MAH is about 1% ~ 3%.
In one embodiment, in described MAH-g-PP, the percentage of grafting of MAH is about 1% ~ 3%.
In one embodiment, in described carboxylated chitosan ,-COOH and-NH
2mol ratio be about 1 ~ 5:1.
In one embodiment, described carboxylated chitosan is selected from one or more in CMC, N-cm-chitosan, N-carboxylic butyl acyl, N-(2-propyloic) chitosan, N-cm-chitosan, 0-cm-chitosan; Preferably, described carboxylated chitosan is 0-cm-chitosan.
In one embodiment, in described raw materials, also containing the potter's clay of 10 ~ 20 weight parts and the zinc oxide of 0.2 ~ 1 weight part.
Another aspect of the present invention provides the preparation method of the recyclable crosslinked TPE tourniquet of environment-friendly type, comprises the following steps:
(1) after described raw material being mixed by weight, through double-screw extruding pelletizing;
(2) by the product of step (1) gained, in about 170 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this injection temperature after 8 hours, then cooling curing obtain.
In one embodiment, the injection temperature in described step (2) is about 195 DEG C.
Of the present inventionly provide on the other hand again the method reclaiming the recyclable crosslinked TPE tourniquet of described environment-friendly type, be placed in the ultraviolet 6 hours that wavelength is less than 360 nanometers, with carboxylated chitosan of degrading by described tourniquet.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised more easily can understand present disclosure.Can mention a large amount of term in following specification sheets and claims, these terms are defined as following implication.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context.
" optional " or " optionally " refers to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification sheets and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
One aspect of the present invention provides environment-friendly type recyclable crosslinked TPE tourniquet, is prepared from by the raw material comprising following weight part:
The term " SEBS " used in the application refers to polystyrene to be end segment, the ethylene-butene copolymer obtained with polyhutadiene hydrogenation is the linear three embedding multipolymers of middle spring block, for the application SEBS and have no special requirements, can be commercially available, also can be obtained by synthesis.
In order to obtain MAH-g-SEBS, in the application, the graft modification of SEBS can adopt solution graft copolymerization and fusion-grafting two kinds of methods, wherein, when solution grafting carries out SEBS grafting MAH, the graft reaction time is long, grafting efficiency is low, needs to consume poisonous, flammable solvent in a large number, and production cost is high, large to human injury, contaminate environment, takes up an area large, is difficult to realize continuous operation.Therefore, preferably melt grafting is adopted.
In one embodiment, in described MAH-g-SEBS, the percentage of grafting of MAH is about 1% ~ 3%.
In order to obtain MAH-g-PP, in the application, the graft modification of PP also can adopt solution graft copolymerization and fusion-grafting two kinds of methods, and preferably adopts melt grafting.
In one embodiment, in described MAH-g-PP, the percentage of grafting of MAH is about 1% ~ 3%.
At present, the chemical modification of chitosan is a key areas of chitosan research, is intended to by-the NH at chitosan
2introduce new functional group with-OH is upper and improves its solvability and other physical chemistry and biology performance.More the having of study on the modification of chitosan: acylations, alkylation, carboxylated, hydroxylation, graft copolymerization, quaternization etc.Wherein, the carboxylated modification of chitosan can be had concurrently-NH
2with the amphoteric chitosan derivative of-COOH, this analog derivative has good water-soluble, surfactivity, film-forming properties, moisture absorbability and moisture retentivity, the biological property such as antibacterial, anti-oxidant, wide application prospect is presented in makeup, food, biological medicine etc., therefore, the carboxylation reaction of chitosan is subject to investigator and more and more pays close attention in recent years." carboxylated chitosan " in the application just by carrying out chemical modification process to common chitosan, and is introduced hydroxy-acid group and is obtained.
In one embodiment, in described carboxylated chitosan ,-COOH and-NH
2mol ratio be about 1 ~ 5:1, amino can react with the anhydride group in MAH-g-SEBS and MAH-g-PP, thus formed crosslinking structure, to improve cross-linking density.
In one embodiment, described-COOH and-NH
2mol ratio be the carboxylated chitosan of about 1 ~ 5:1 be selected from CMC, N-cm-chitosan, N-carboxylic butyl acyl, N-(2-propyloic) chitosan, N-cm-chitosan, 0-cm-chitosan one or more; Preferably, described-COOH and-NH
2mol ratio be about 2:1, and described carboxylated chitosan is 0-cm-chitosan.
Another aspect of the present invention provides the preparation method of the recyclable crosslinked TPE tourniquet of environment-friendly type, comprises the following steps:
(1) after described raw material being mixed by weight, through double-screw extruding pelletizing;
(2) by the product of step (1) gained, in about 170 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this temperature after 8 hours, then cooling curing obtain.
In one embodiment, the injection temperature in described step (2) is about 195 DEG C.
Applicant is surprised to find that, by vacuum injection also under vacuum, keeps pyroprocessing, can improve the cross-linking density of tourniquet further.This is due to graphene oxide containing a large amount of carboxyls; at high temperature and under the condition of vacuum hydro-extraction; can with the phenyl ring generation friedel-crafts acylation on styrene units in SEBS and MAH-g-SEBS, thus occur further crosslinked, to provide Advantageous Effects of the present invention.
Of the present inventionly provide on the other hand again the method reclaiming the recyclable crosslinked TPE tourniquet of described environment-friendly type, be placed in the ultraviolet 6 hours that wavelength is less than 360 nanometers, with carboxylated chitosan of degrading by described tourniquet.
Ultraviolet also can cause DeR to the irradiation of chitosan, is commonly called as photodegradation.Dominant mechanism is: light is absorbed by H2O2, accelerates the photodissociation of peroxidation key, creates hydroxyl radical free radical, β-D-(Isosorbide-5-Nitrae) glycosidic link of effect chitosan, destroys glucosides link subsequently, makes degradation of chitosan.Therefore, the degraded of described carboxylated chitosan can reduce the cross-linking density of tourniquet, thus makes the tourniquet after process have cycling processability, to provide beneficial effect of the present invention.
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, raw materials used is all commercially available, and following material number used is weight part.
Raw material:
A1：SEBS
A2:MAH-g-SEBS (percentage of grafting of MAH is 1%)
A3:MAH-g-SEBS (percentage of grafting of MAH is 3%)
B1：PP
B2:MAH-g-PP (percentage of grafting of MAH is 1%)
B3:MAH-g-PP (percentage of grafting of MAH is 3%)
C1: carboxylated chitosan (N-cm-chitosan ,-COOH and-NH
2mol ratio be about 1:1)
C2: carboxylated chitosan (N-cm-chitosan ,-COOH and-NH
2mol ratio be about 5:1)
C3: carboxylated chitosan (N-cm-chitosan ,-COOH and-NH
2mol ratio be about 2:1)
C4: carboxylated chitosan (N-cm-chitosan ,-COOH and-NH
2mol ratio be about 2:1)
C5: carboxylated chitosan (0-cm-chitosan ,-COOH and-NH
2mol ratio be about 2:1)
D1: white oil
E1: potter's clay
F1: zinc oxide
Embodiment 1 ~ 8 and comparative example 1:
The recyclable crosslinked TPE tourniquet of environment-friendly type is prepared, preparation method's following (consumption of following component is parts by weight) according to the formula in following table 1:
(1) after described raw material being mixed by weight, through double-screw extruding pelletizing;
(2) by the product of step (1) gained, in 195 DEG C of vacuum injections in mould, and under vacuum, keep this temperature after 8 hours, then cooling curing obtain.
Comparative example 2 (not adopting vacuum injection):
The recyclable crosslinked TPE tourniquet of environment-friendly type is prepared, preparation method's following (consumption of following component is parts by weight) according to the formula in following table:
(1) after described raw material being mixed by weight, through double-screw extruding pelletizing;
(2) by the product of step (1) gained, in 195 DEG C of vacuum injections in mould, keep this temperature after 8 hours, then cooling curing obtain.
Above-described embodiment 1 ~ 8 and comparative example 2 gained tourniquet are placed in wavelength and are less than the ultraviolet of 360 nanometers after 6 hours, more again process, find that it all has good cycling processability.
The composition of raw materials that table 1 is the recyclable crosslinked TPE tourniquet of preparation environment-friendly type and consumption (parts by weight)
testing method
Tensile property: tensile strength and elongation at break measure according to JIS K6251.
Rebound performance: according to JIS K6251, by made sample repeated stretching 100 times, tensile elongation is five times of former state, and calculates its longitudinal absolute deformation amount and assess.
Test result is in table 2.
Table 2
| Example | Tensile strength (MPa) | Elongation at break (%) | Absolute deformation amount (%) |
| Embodiment 1 | 14.4 | 825 | 3.6 |
| Embodiment 2 | 13.6 | 801 | 3.2 |
| Embodiment 3 | 17.0 | 813 | 3.0 |
| Embodiment 4 | 16.5 | 786 | 2.6 |
| Embodiment 5 | 15.8 | 796 | 2.9 |
| Embodiment 6 | 17.1 | 775 | 2.3 |
| Embodiment 7 | 20.3 | 752 | 2.0 |
| Embodiment 8 | 21.1 | 766 | 2.2 |
| Comparative example 1 | 9.5 | 850 | 4.5 |
| Comparative example 2 | 12.4 | 845 | 2.5 |
Above data can be found out, compared with the product not using carboxylated chitosan and do not adopt vacuum injection, medical TPE tourniquet of the present invention has better tensile strength and screen resilience, meanwhile, it can also reclaim and reprocess, environmental-protecting performance is superior, because herein is provided Advantageous Effects of the present invention.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. the recyclable crosslinked TPE tourniquet of environment-friendly type, is characterized in that, be prepared from by the raw material comprising following weight part:
2. the recyclable crosslinked TPE tourniquet of environment-friendly type as claimed in claim 1, it is characterized in that, in described MAH-g-SEBS, the percentage of grafting of MAH is about 1% ~ 3%.
3. the recyclable crosslinked TPE tourniquet of environment-friendly type as claimed in claim 1, it is characterized in that, in described MAH-g-PP, the percentage of grafting of MAH is about 1% ~ 3%.
4. the recyclable crosslinked TPE tourniquet of environment-friendly type as claimed in claim 1, is characterized in that, in described carboxylated chitosan, and-COOH and-NH
2mol ratio be about 1 ~ 5:1.
5. the recyclable crosslinked TPE tourniquet of environment-friendly type as claimed in claim 4, it is characterized in that, described carboxylated chitosan is selected from one or more in CMC, N-cm-chitosan, N-carboxylic butyl acyl, N-(2-propyloic) chitosan, N-cm-chitosan, 0-cm-chitosan.
6. the recyclable crosslinked TPE tourniquet of environment-friendly type as claimed in claim 5, it is characterized in that, described carboxylated chitosan is 0-cm-chitosan.
7. the recyclable crosslinked TPE tourniquet of the environment-friendly type according to any one of claim 1 ~ 6, is characterized in that, in described raw materials, also containing the potter's clay of 10 ~ 20 weight parts and the zinc oxide of 0.2 ~ 1 weight part.
8. prepare the method for the recyclable crosslinked TPE tourniquet of environment-friendly type, it is characterized in that, comprise the following steps:
(1) by the raw material according to any one of claim 1 ~ 7, by weight after mixing, through double-screw extruding pelletizing;
(2) by the product of step (1) gained, in about 170 DEG C ~ 200 DEG C vacuum injections in mould, and under vacuum, keep this injection temperature after 8 hours, then cooling curing obtain.
9. prepare the method for the recyclable crosslinked TPE tourniquet of environment-friendly type as claimed in claim 8, it is characterized in that, the injection temperature in described step (2) is about 195 DEG C.
10. reclaim the method for the recyclable crosslinked TPE tourniquet of environment-friendly type according to any one of claim 1 ~ 7, it is characterized in that, described tourniquet is placed in the ultraviolet 6 hours that wavelength is less than 360 nanometers, with carboxylated chitosan of degrading.
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| CN105086323A (en) * | 2015-09-07 | 2015-11-25 | 安徽雄亚塑胶科技有限公司 | High-strength halogen-free and flame-retardant TPE (thermoplastic elastomer) cable material and preparation method thereof |
| CN105219008A (en) * | 2015-10-10 | 2016-01-06 | 嘉兴市博尔塑胶有限公司 | A kind of composition of SEBS reclaimed materials and by its obtained automobile SEBS ground cushion |
| CN105367973A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | High-performance environment-friendly TPE plastic wrap and preparation method thereof |
| CN105367974A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | Low temperature resistant TPE composition and ice cube tray prepared therefrom |
| CN105383347A (en) * | 2015-11-18 | 2016-03-09 | 安徽雄亚塑胶科技有限公司 | High-performance TPE (Thermal Plastic Elastomer) vehicle foot pad and preparation method thereof |
| CN106928621A (en) * | 2017-04-20 | 2017-07-07 | 苏州康邦新材料有限公司 | Woven hose TPE and preparation method thereof |
| CN106987080A (en) * | 2017-04-20 | 2017-07-28 | 苏州康邦新材料有限公司 | TPE tourniquets and preparation method thereof |
| CN118307926A (en) * | 2024-05-13 | 2024-07-09 | 惠州市启达环美科技有限公司 | Weather-proof and anti-burst material for plastic plants and preparation method thereof |
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| CN106987080B (en) * | 2017-04-20 | 2019-09-13 | 苏州康邦新材料有限公司 | TPE tourniquet and preparation method thereof |
| CN118307926A (en) * | 2024-05-13 | 2024-07-09 | 惠州市启达环美科技有限公司 | Weather-proof and anti-burst material for plastic plants and preparation method thereof |
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