CN101486818A - Thermoplastic elastomer materials - Google Patents
Thermoplastic elastomer materials Download PDFInfo
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- CN101486818A CN101486818A CNA2008100327997A CN200810032799A CN101486818A CN 101486818 A CN101486818 A CN 101486818A CN A2008100327997 A CNA2008100327997 A CN A2008100327997A CN 200810032799 A CN200810032799 A CN 200810032799A CN 101486818 A CN101486818 A CN 101486818A
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Abstract
The invention provides a thermoplastic elastomer material which consists of the following ingredients according to weight percentage: (A) 30-80% of polyolefin resin and 20-70% of hydriding styrenic thermoplastic elastomer. The MFR of the polyolefin resin is 2-7, which is measured according to ISO1133 standard (the temperature is 230 DEG C, the load is 2.16kg). The thermoplastic elastomer material is obtained by mixing the ingredient (A) and the ingredient (B) at the melt temperature of 210-220 DEG C and the screw speed of 300-450rpm.
Description
Technical field
The present invention relates to polymeric material field, relate to a kind of thermoplastic elastic material particularly.
Background technology
PVC contains halogen and is unfavorable for HUMAN HEALTH, when making the PVC articles for use, need add 20-50% dimixo-octyl phthalate softening agent (DEHP) simultaneously as softening agent, DEHP and other phthalic acid ester classes are environment female hormone class material, can cause problems such as the increase of female mammary gland cancer morbidity, the decline of male genetic power, teenager's heteroplasia.When making medical device with the PVC material as the transfusion articles for use, easily stripping in medicament of DEHP, serious harm HUMAN HEALTH.And PVC also can not be ignored the influence of ecotope, burning below 600 ℃ or buried processing, all can produce Dioxins, and DEHP do not degrade for a long time, continues to influence human health.Along with appearing of soft PVC product defect, in the world its restriction and the cry of eliminating are also increased thereupon.
On medical device was especially infused with goods, the non-PVC-soft-bag transfusion not only had the advantage of PVC soft bag infusion, but also has overcome the shortcoming of PVC soft bag infusion.Non-PVC-soft-bag transfusion is a complete closed formula packing, plasticizer-containing (DEHP) not, and good stability, drug compatibility are good, and the water-permeable ventilation property is extremely low, can degrade at nature, can not cause big harm to environment, human body.
Aspect industrial use, substitute the PVC material, the present situation of industrial non-PVC plastic material is to use the blend of TPE+ treated oils such as hydrogenated styrene thermoplastic elastomer such as SEBS both at home and abroad.Though the price of SEBS is higher than conventional rubber, because it has processed edge, the overall cost of end article is lower; In addition, because it has ageing-resistant performance, and processing capable of circulation, be a kind of environment-friendly materials of recyclable utilization.SEBS can obtain the resilient material of high rigidity through processing, can be used to production engineering high modulus thermoplastic elastomer product, at electric wire and cable jacket, sealing article, penetrate field such as sizing and substitute vulcanized rubber just gradually.Since nontoxic and human body is not produced rejection, be very suitable for the production of toy for children again.The plastic material of TPE+ treated oils such as SEBS has poor heat resistance, intensity is low, treated oil is easily separated out and shortcoming such as transparency difference.Along with the raising of people's living standard, the requirement of luxury goods is also increased, the material of common SEBS+ treated oil is not because the limitation of its performance has satisfied people's demand.
In sum, this area lacks a kind of no any plasticizer, no treated oil, and the thermoplastic elastic material of high-strength and high-transparent, therefore, this area presses for develops a kind of transparent novel cpd of innage that do not have.
Summary of the invention
The objective of the invention is to obtain a kind of no any plasticizer, do not have any treated oil, the novel thermoplastic elastomer of high-strength and high-transparent.
A further object of the present invention is to obtain a kind of no any plasticizer, does not have any treated oil, the preparation method of the novel thermoplastic elastomer of high-strength and high-transparent.
A further object of the invention is to obtain a kind of goods of novel thermoplastic elastomer of the present invention.
First aspect present invention provides a kind of thermoplastic elastic material, and described material is made by following component:
(A) polyolefin resin component 30～80 weight %, the MFR of wherein said polyolefin resin is 2～7, according to ISO1133 (230 ℃ of temperature, load 2.16Kg) standard test;
(B) hydrogenated styrene thermoplastic elastomer component 20～70 weight %;
The mixture of said components (A) and component (B) is carried out mixing, when mixing melt temperature 210-220 ℃; Screw speed 300-450rpm obtains described thermoplastic elastic material.
In a specific embodiment of the present invention, described component (A) polyolefin resin component is selected from random copolymerization PP or reactor (reactivity) PP.
In a specific embodiment of the present invention, described component (B) hydrogenated styrene thermoplastic elastomer component is selected from hydrogenated styrene/Butadiene segmented copolymer.
In a specific embodiment of the present invention, the transmittance of resulting thermoplastic elastic material is not less than 98%, is 50% in room temperature, humidity, thickness is to adopt GB2410-80 determination of light transmittance standard to measure under the 200 μ m.
In a specific embodiment of the present invention, resulting thermoplastic elastic material does not contain treated oil and plasticizer components.
In a specific embodiment of the present invention, the mixture of said components (A) and component (B) is carried out when mixing, described compounding process adopts the twin screw extrusion molding.
The present invention provides a kind of preparation methods of the present invention on the other hand, it is characterized in that, comprises the steps:
(a) provide polyolefin component polyolefin resin component 30～60 weight %, the mixture of hydrogenated styrene thermoplastic elastomer component 40～70 weight % in composition total weight; The MFR of wherein said polyolefin resin is 2～7, according to ISO1133 (230 ℃ of temperature, load 2.16Kg) standard test;
(b) mixture of step (a) is carried out mixing, obtain described thermoplastic elastic material; Melt temperature 210-220 when wherein mixing ℃; Screw speed 300-450rpm.
In a specific embodiment of the present invention, the mixing employing twin screw extrusion molding of described step (b).
In another aspect of the present invention, a kind of goods of thermoplastic elastomer (s) are provided, described goods are selected from medical device.
In a specific embodiment of the present invention, described medical device is an infusion bag with film or tubing.
Embodiment
The inventor is through extensive and deep research, by improving preparation technology, obtained just can obtain without any need for treated oil and softening agent the thermoplastic elastomer material composition and the thermoplastic elastic material thereof of good transparency and anti-discounting.Finished the present invention on this basis.
Among the present invention, term " contains " or the various compositions of " comprising " expression can be applied in mixture of the present invention or the composition together.Therefore, term " mainly by ... form " and " by ... composition " be included in that term " contains " or in " comprising ".
(A) polyolefin resin component
As used herein, described " polyolefin resin " except as otherwise noted, refers to by polymerization and contains the polyolefine that the olefinic monomer of polymerizable double bond obtains.Polyolefine of the present invention can be a homopolymer, for example Alathon, alfon.
Preferred random copolymerization PP of the polyolefinic example that described degree of crystallinity is lower or reactor PP are best.Described random copolymerization PP is for example W331 (MFR is 7) that produces of polyolefins company (TPC) and S331 (also claim SPG165, MFR is 2) etc. particularly.Described reactor (reactivity) PP can adopt this area reactorPP commonly used, particularly the Eccelene EP3711E1 that produces of Sumitomo Chemical etc. for example.
(A) part by weight of polyolefin resin component is 30～80 weight %, and preferred 30～60 weight % are with the total weight of material.The MFR of wherein said polyolefin resin is 2～7, and described MFR is according to ISO1133 (230 ℃ of temperature, load 2.16Kg) standard test.
(B) hydrogenated styrene thermoplastic elastomer component
Hydrogenated styrene thermoplastic elastomer of the present invention can adopt hydrogenated styrene thermoplastic elastomer traditional in this area, normally by vinylbenzene and conjugated diene copolymer elastomerics are carried out the thermoplastic elastomer that hydrogenation obtains.Described conjugated diolefine for example is isoprene, divinyl or its combination, but is not limited thereto.Described hydrogenant degree and hydrogenant position are not particularly limited.
Preferably, described hydrogenated styrene thermoplastic elastomer is hydrogenated styrene/Butadiene segmented copolymer (SEBS).Described hydrogenated styrene/Butadiene segmented copolymer can adopt the traditional hydrogenated styrene in this area/Butadiene segmented copolymer.
Example includes but not limited to particularly:
The analogous products such as H3151 that Taiwan synthetic rubber (TSRC) is produced;
Rise the analogous products such as G1651 that (Kraton) produces as section;
Produce SEPTON as Kuraray (Kuraray)
TM8006, HYBRAR7311 etc.
The consumption of hydrogenated styrene thermoplastic elastomer component is 20～70 weight % among the present invention, and preferred 40～70 weight % are with the material total weight.
In prior art combinations, in order to reach corresponding transmittance, must add a lot of small-molecule substances, for example treated oil and softening agent greater than 98%.And in some specific field, medical field for example, these small-molecule substances in use can discharge, and human body is produced injury.
And the characteristics of material of the present invention are, can be under the situation of no any treated oil and softening agent, still reach transmittance greater than 98% effect.
Described treated oil comprises the treated oil that adopt traditionally in order to reach transparency this area, comprises alkane oil, naphthenic oil or aromatic hydrocarbon oil.
Described softening agent comprises the plasticizing adjuvant that adopt traditionally this area, includes but not limited to dimixo-octyl phthalate (DEHP).
Though material of the present invention only contain component (A) and (B), do not contain treated oil and softening agent, still reached transmittance greater than 98% effect.Meet of the particular requirement of some specific field to transparency.
Be not specifically limited by preparation of compositions of the present invention preparation methods of the present invention, only otherwise goal of the invention of the present invention is produced restriction to get final product, for example adopt methods such as mixing particularly.
Particularly for example: comprise the steps:
(a) provide polyolefin component 30～60 weight %, hydrogenated styrene thermoplastic elastomer component 40～70 weight % in composition total weight; The MFR of wherein said polyolefin resin is 2～7, according to ISO1133 (230 ℃ of temperature, load 2.16Kg) standard test;
(b) mixture of step (a) is carried out mixing, obtain described thermoplastic elastic material.
Preferably, the mixing employing twin screw extrusion molding of described step (b), more preferably, the processing condition of described twin screw extrusion molding are melt temperature 210-220 ℃; Screw speed 300-450rpm.
In sum, the present invention does not have the high transparent type material advantage of oil type and is:
(1) material of the present invention does not contain any oil (as alkane oil, naphthenic oil and aromatic hydrocarbons wet goods), and this is the basic part of other TPE materials of difference (also being the thermoplastic elastomer material).
(2) material of the present invention realizes that height is transparent under the prerequisite of not using any oil, and this is the basic part of other TPE materials of difference.
(3) the no oil of material of the present invention is transparent, the intensity height, and softness, anti-discounting is better, and good heat resistance, good weatherability.
(4) material of the present invention does not contain any oil (as alkane oil, naphthenic oil and aromatic hydrocarbons wet goods), so chemical resistance is good, and anti-appearance agent is good.
Goods
Material of the present invention can be applied to the goods in various fields.
Material of the present invention is specially adapted to the conditional goods of the small-molecule substance in the material, for example medical device etc.For example, material of the present invention can be used for replacing PVC, and TPU and some are traditional contains oil type TPE material etc., is widely used in medical device such as tubing, and the mould material that infusion bag is used also can be used as infusion bottle and other transfusion with device such as stype etc.
Major advantage of the present invention is as follows:
(1) the TPE material of above-mentioned composition does not contain additives such as any treated oil (as alkane oil, naphthenic oil and aromatic hydrocarbons wet goods) and softening agent, and chemical resistance is good, and solvent resistance is good, weathering resistance and good heat resistance.This is not available characteristics such as other TPE materials (as oil-filled blends such as SEBS, TPU etc.) and pvc material.
(2) the TPE material of above-mentioned composition is realized high transparent under the prerequisite that does not contain additives such as any treated oil (as alkane oil, naphthenic oil and aromatic hydrocarbons wet goods) and softening agent.This also is that this is not available characteristics such as other TPE materials (as oil-filled blends such as SEBS, TPU etc.) and pvc material.
(3) the TPE material of above-mentioned composition has anti-preferably discounting under the prerequisite that does not contain additives such as any treated oil (as alkane oil, naphthenic oil and aromatic hydrocarbons wet goods) and softening agent.This also is that this is the not available characteristics of other TPE materials (as blends such as oil-filled SEBS etc.).
(4) the TPE material of above-mentioned composition is not owing to contain additives such as any treated oil (as alkane oil, naphthenic oil and aromatic hydrocarbons wet goods) and softening agent, intensity height.This also is that this is the not available characteristics of other TPE materials (as blends such as oil-filled SEBS etc.).
Above-mentioned preparation method is the synthetic route of part of compounds of the present invention, according to above-mentioned example, those skilled in the art can prepare other raw materials of the present invention by adjusting diverse ways, and perhaps, those skilled in the art can prepare raw material of the present invention according to existing known technology.
Other aspects of the present invention are because the disclosure of this paper is conspicuous to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage.
Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any in addition method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
Prescription:
Random PP (S331)/HYBRAR7311 (Kuraray company)=60/40 (weight proportion, as follows)
The MFR of described random PP (S331) is 2
Mixing condition:
Device name; Twin screw extruder (CTE-75, screw diameter D72mm, L/D are 32-56, times Long Keya of section produces)
When mixing melt temperature 210-220 ℃; Screw speed 300-450rpm
Step:
The random PP (S331) of described prescription is mixed with HYBRAR7311, and the mixture that obtains places described twin screw basis machine at melt temperature 210-220 ℃; Extrude under the screw speed 300-450rpm, obtain thermoplastic elastic material.
The hardness 75A of above-mentioned blend, tensile strength 25MPa, elongation at break 650%, MFR1.5, transmittance can be used on tubing greater than 98%, the mould material that infusion bag is used etc.
Hardness measuring method: ISO7619
Tensile test method: ISO37, room temperature, rate of extension 150mm/min
Melt flow index testing method: IS01133,230 ℃, 2.16Kg
The transmittance testing method: normal temperature, thickness are 200 μ m
Embodiment 2
The method of embodiment 2 is identical with embodiment 1, and difference is:
Prescription, reactor PP (EP3711E1)/HYBRAR7311=70/30
The MFR of described reactor PP (EP3711E1) is 7
Mixing condition
Device name; Twin screw extruder (CTE-75, screw diameter D72mm, L/D are 32-56, times Long Keya of section produces)
When mixing melt temperature 210-220 ℃; Screw speed 300-450rpm
The hardness 73A of above-mentioned blend, tensile strength 26MPa;
Elongation at break 660%, MFR2.0, transmittance can be used on tubing greater than 98%, the mould material that infusion bag is used etc.
Hardness measuring method: ISO7619
Tensile test method: ISO37, room temperature, rate of extension 150mm/min
Melt flow index testing method: ISO1133,230 ℃, 2.16Kg
The transmittance testing method: normal temperature (25 ℃), thickness are 200 μ m
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. a thermoplastic elastic material is characterized in that, described material is made by following component:
(A) polyolefin resin component 30～80 weight %, the melt flow index mfr of wherein said polyolefin resin is 2～7, according to ISO1133 (230 ℃ of temperature, load 2.16Kg) standard test;
(B) hydrogenated styrene thermoplastic elastomer component 20～70 weight %;
The mixture of said components (A) and component (B) is carried out mixing, when mixing melt temperature 210-220 ℃; Screw speed 300-450rpm obtains described thermoplastic elastic material.
2. material as claimed in claim 1 is characterized in that,
Described component (A) polyolefin resin component is selected from random copolymerization PP or reactor (reactivity) PP.
3. material as claimed in claim 1 is characterized in that, described component (B) hydrogenated styrene thermoplastic elastomer component is selected from hydrogenated styrene/Butadiene segmented copolymer.
4. material as claimed in claim 1 is characterized in that the transmittance of resulting thermoplastic elastic material is not less than 98%, is 50% in room temperature, humidity, thickness is to adopt GB2410-80 determination of light transmittance standard to measure under the 200 μ m.
5. material as claimed in claim 1 is characterized in that resulting thermoplastic elastic material does not contain treated oil and plasticizer components.
6. material as claimed in claim 1 is characterized in that, the mixture of said components (A) and component (B) is carried out when mixing, and described compounding process adopts the twin screw extrusion molding.
7. a preparation methods as claimed in claim 1 is characterized in that, comprises the steps:
(a) provide polyolefin component polyolefin resin component 30～60 weight %, the mixture of hydrogenated styrene thermoplastic elastomer component 40～70 weight % in composition total weight; The MFR of wherein said polyolefin resin is 2～7, according to ISO1133 (230 ℃ of temperature, load 2.16Kg) standard test;
(b) mixture of step (a) is carried out mixing, obtain described thermoplastic elastic material; Melt temperature 210-220 when wherein mixing ℃; Screw speed 300-450rpm.
8. method as claimed in claim 7 is characterized in that, the mixing employing twin screw extrusion molding of described step (b).
9. the goods of a material as claimed in claim 1 is characterized in that, described goods are selected from medical device.
10, goods as claimed in claim 9 is characterized in that, described medical device is an infusion bag with film or tubing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100327997A CN101486818A (en) | 2008-01-18 | 2008-01-18 | Thermoplastic elastomer materials |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100327997A CN101486818A (en) | 2008-01-18 | 2008-01-18 | Thermoplastic elastomer materials |
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| CN101486818A true CN101486818A (en) | 2009-07-22 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102883698A (en) * | 2010-06-22 | 2013-01-16 | 三菱化学株式会社 | Rubber stopper for medical use |
| CN104086905A (en) * | 2014-07-25 | 2014-10-08 | 北京奥星医药耗材有限公司 | Modified polypropylene soft bottle material, as well as preparation method and applications thereof |
| CN104349890A (en) * | 2012-06-06 | 2015-02-11 | 美国圣戈班性能塑料公司 | Thermoplastic elastomer tubing and method to make and use same |
| CN104419065A (en) * | 2013-09-03 | 2015-03-18 | 辽宁九洲龙跃药业有限公司 | Polypropylene-blended soft infusion bag and preparation method thereof |
| CN104448668A (en) * | 2013-09-12 | 2015-03-25 | 上海康德莱企业发展集团股份有限公司 | TPE material for medical infusion device tube and preparation method thereof |
| CN104497415A (en) * | 2014-11-28 | 2015-04-08 | 湖北恒泰橡塑有限公司 | Thermoplastic elastomer for transfusion bag and preparation method of thermoplastic elastomer for transfusion bag |
| WO2018036132A1 (en) * | 2016-08-24 | 2018-03-01 | 南通普力马弹性体技术有限公司 | Solvent-bonding twisting-resistant transparent transfusion tube material |
| US11365311B2 (en) | 2019-12-31 | 2022-06-21 | Industrial Technology Research Institute | Flexible transparent material |
-
2008
- 2008-01-18 CN CNA2008100327997A patent/CN101486818A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102883698B (en) * | 2010-06-22 | 2015-03-25 | 三菱化学株式会社 | Rubber stopper for medical use |
| CN102883698A (en) * | 2010-06-22 | 2013-01-16 | 三菱化学株式会社 | Rubber stopper for medical use |
| US9080044B2 (en) | 2010-06-22 | 2015-07-14 | Mitsubishi Chemical Corporation | Rubber stopper for medical treatment |
| US9987784B2 (en) | 2012-06-06 | 2018-06-05 | Saint-Gobain Performance Plastics Corporation | Thermoplastic elastomer tubing and method to make and use same |
| CN104349890A (en) * | 2012-06-06 | 2015-02-11 | 美国圣戈班性能塑料公司 | Thermoplastic elastomer tubing and method to make and use same |
| CN104419065A (en) * | 2013-09-03 | 2015-03-18 | 辽宁九洲龙跃药业有限公司 | Polypropylene-blended soft infusion bag and preparation method thereof |
| CN104448668A (en) * | 2013-09-12 | 2015-03-25 | 上海康德莱企业发展集团股份有限公司 | TPE material for medical infusion device tube and preparation method thereof |
| CN104086905A (en) * | 2014-07-25 | 2014-10-08 | 北京奥星医药耗材有限公司 | Modified polypropylene soft bottle material, as well as preparation method and applications thereof |
| CN104086905B (en) * | 2014-07-25 | 2017-01-18 | 雷诺丽特塑料科技（北京）有限公司 | Modified polypropylene soft bottle material, as well as preparation method and applications thereof |
| CN104497415A (en) * | 2014-11-28 | 2015-04-08 | 湖北恒泰橡塑有限公司 | Thermoplastic elastomer for transfusion bag and preparation method of thermoplastic elastomer for transfusion bag |
| CN104497415B (en) * | 2014-11-28 | 2017-07-21 | 湖北恒泰橡塑有限公司 | Infusion bag thermoplastic elastomer (TPE) and preparation method thereof |
| WO2018036132A1 (en) * | 2016-08-24 | 2018-03-01 | 南通普力马弹性体技术有限公司 | Solvent-bonding twisting-resistant transparent transfusion tube material |
| US11365311B2 (en) | 2019-12-31 | 2022-06-21 | Industrial Technology Research Institute | Flexible transparent material |
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Open date: 20090722 |