CN104693665A - Thermoplastic water-swellable elastomer and preparing method and application thereof - Google Patents
Thermoplastic water-swellable elastomer and preparing method and application thereof Download PDFInfo
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- CN104693665A CN104693665A CN201510161293.6A CN201510161293A CN104693665A CN 104693665 A CN104693665 A CN 104693665A CN 201510161293 A CN201510161293 A CN 201510161293A CN 104693665 A CN104693665 A CN 104693665A
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Abstract
The invention relates to a thermoplastic water-swellable elastomer and a preparing method and application thereof and belongs to the technical field of rubber products. The thermoplastic elastomer is used for water resistance, leaking stoppage and sealing. Water-swellable rubber comprises, by weight, 100 parts of thermoplastic elastomer, 20-60 parts of water absorbing material, and 1-20 parts of ionomer resin. The preparing method of the water-swellable elastomer comprises the steps of conducting plastication and fusion on the thermoplastic elastomers, adding the water absorbing materials and ionomer resin in the plasticated object for shearing blending, and conducting secondary plastication to obtain the high-performance thermoplastic water-swellable elastomer. The water-swellable elastomer has excellent mechanical property and can expand by multiple times or even hundred of times of the mass or volume of itself after absorbing water, preparing process is simple and continuous, large-scale production can be achieved, and repeated forming and machining can be achieved.
Description
Technical field
The invention belongs to rubber item technical field, be specifically related to a kind of to there is high performance thermoplasticity uptake model repeating molding processibility and its preparation method and application.
Background technology
Water swelling rubber (Water-swellable Rubber, be called for short WSR) be a kind of novel functional high molecule material, it in thermoplastic elastic body matrix, add a certain amount of water-absorbing material and other fillers are prepared from, it can rubber be elastomeric has quick water-retaining capacity simultaneously in maintenance, and under extraneous squeezed state, still there is stronger water retention capacity, when WSR contacts with water, can water molecules be absorbed in rubber matrix, volume expands, the swelling pressure produced can play the effect of sealing leak stopping, the i.e. dual sealing characteristic of hydroscopic water-resisting and water-swelling sealing.
Water swelling rubber is being described as by anti-hydrosphere " double insurance sealing material " and " super seal material " in 20 century 70s.WSR is very easy in application aspect, efficiency is high, can save material and reduce construction costs, is the waterproof and sealing material of replacement type, has good application prospect and huge market.External research starting in the preparation, performance etc. of WSR comparatively early, and produced this series products of a large amount of high-quality, and only have minority producer to possess the ability of production high-quality water swelling rubber at home, quality and performance exists certain gap with external product, and research further of still needing is with perfect.At present, on market, business-like water swelling rubber is thermoset rubber, once after forming process, its matrix is namely in tridimensional network, and can not carry out forming process again, this not too meets the aim of environmental protection shaped material.At present, exploitation has the water swelling rubber that can repeat forming process has become new research and development direction, water uptake expansion material field.
On the other hand, because rubber matrix is generally nonpolar hydrophobic and absorbent composition is hydrophilic component mostly, consistency between two components is poor, make shaping after goods performance reduce, especially after water-swelling, part absorbent composition can be separated out, and mechanical property also can significantly decline, this severely limits the field of water swelling rubber application, make it can only be used for the Working environment of simple water blockoff or lower pressure.
Summary of the invention
In view of above problem, the present invention adopts the ionomeric mode of interpolation three components, by the selection of thermoplastic matrix, and by introducing water-absorbing material in matrix phase, develop a kind of excellent mechanical performances and high water-swelling multiplying power, and there is the preparation method of the novel thermoplastic uptake model that can repeat moulding processability.
Concrete technical scheme is as follows:
A kind of thermoplasticity uptake model, described elastomerics comprises the component of following weight part:
Described thermoplastic elastomer is selected from the combination of one or more in styrene-butadiene one styrene block copolymer (SBS), acrylonitrile-butadiene-styrene copolymer (ABS), thermoplastic polyurethane (TPU), polyolefin elastomer (POE), ethylene-vinyl acetate copolymer (EVA), thermoplastic polyester elastomer (TPEE).
Described water-absorbing material is selected from the combination of one or more in starch-series water-absorbing material, cellulose-based water-absorbing material and synthetic resins system water-absorbing material.
Described ionomer resin is Du Pont
the combination of one or more in W 501NC, Honeywell low molecule ionomer AClyn, Du Pont Surlyn, Tao Shi AMPLIFY IO 3701, Du Pont FORMION.
Metal ion in described ionomer resin comprises Zn
2+, Na
+, K
+, Li
+.
Described oxidation inhibitor is selected from antioxidant 2246, antioxidant 1010, oxidation inhibitor 4426, antioxidant 1076, antioxidant 300.
The preparation method of above-mentioned arbitrary described thermoplasticity uptake model, comprises following steps:
First, by the pre-mixing 1 ~ 10 minute in high-speed mixer of described thermoplastic elastomer and described oxidation inhibitor, pre-composition is obtained; After described pre-composition is added high-temperature mixer, at 160 ~ 230 DEG C, melting is plasticated 5 ~ 20 minutes, obtains melts;
Then, in described melts, add described ionomer resin, melting is sheared 1 ~ 5 minute, then adds described water-absorbing material melt blending 7 ~ 10 minutes, obtains mixing thing;
Finally, described mixing thing is carried out cooling and dicing after secondary plasticizing, the temperature of secondary plasticizing is 170 ~ 220 DEG C, and rotating speed is 60 ~ 120rpm, obtains described thermoplasticity uptake model.
The application of above-mentioned arbitrary described thermoplasticity uptake model, for waterproofing and leakage-stopping and hermetic seal, comprise the job facilities such as waterproofing and leakage-stopping engineering, subway, culvert, building construction, also can be used on the fields such as water-sensitive sensor, biomaterial for medical purpose, soil improvement agent and water-holding agent simultaneously and use.
The present invention has the following advantages: from integral part, owing to there being ionomeric existence, the main chain of its uniqueness is nonpolar, the structure of side chain ionic group makes it can play the effect of expanding material between rubber phase with water-absorbing material phase, solve the problem that its water-absorbing material is easily deviate from, and this kind of thermoplastic elastomers has good fatigue performance, use and good resistance to ultraviolet, weather resistance under being particluarly suitable for the condition of repeatedly repeated loading; Moreover from preparation method, being different from general take rubber as the water uptake expansion material of matrix, take thermoplastic elastomer as the feature that the water uptake expansion material of matrix has post forming, and processing is simple, need not sulfuration, can continuous prodution, can give goods good feasibility of batch preparation.
Embodiment
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is that 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 professional and technical personnel's content according to the present invention in this field is made, still belong to protection scope of the present invention.
Embodiment 1
(1) before experiment, by 100 parts per weight of thermoplastic's elastomericss, 30 parts by weight of polypropylene acid sodium water-absorbing materials and 5 parts
w 501NC ionomer resin dries 4 hours under 90 DEG C of conditions.
(2) at room temperature, 100 parts per weight of thermoplastic's elastomericss are mixed 5 minutes with 0.5 weight part oxidation inhibitor in high-speed mixer, rotating speed is that 800rpm obtains just mixed thing.
(3) then at 180 DEG C, described pre-composition is added in Banbury mixer and carry out melting and plasticate 20 minutes, then add 5 weight part ionomer resins
w 501NC carries out melting and shears 10 minutes; Finally add sodium polyacrylate 30 weight part, mixing 15 minutes, obtain mixing thing; Again added in single screw extrusion machine by product after mixing and carry out secondary plasticizing and cooling and dicing, temperature is 180 DEG C, and rotating speed is 60rpm, obtains high-performance thermoplastic uptake model.
(4) utilize injection moulding machine injection moulding for the batten of mechanical test, injection moulding machine each section of temperature is 195 ~ 215 DEG C.
According to Standard, following mechanical test is carried out for the injection moulding batten obtained:
The test of cross-linked rubber tensile stress-strain performance is carried out according to GB/T 528-1998.Test sample is dumbbell shape sample, sample overall length 75mm, presss from both sides pitch spacing from 45mm, gauge length 20mm, draw speed 500mm/min.
Tear resistance test is carried out according to GB/T 528-2008.Draw speed 500mm/min.
All samples before testing, constant temperature 24 hours under 25 DEG C of constant temperatures.Probe temperature is 25 DEG C.
Water-swelling is tested: specimen size is 20 × 20 × 2mm, under room temperature condition, be soaked in after sample is weighed in deionized water, soak to take out after 96 hours and weigh, blot the moisture of specimen surface when weighing gently with thieving paper, the calculation formula of expansion rate of water absorption is as follows:
Sample weight × 100% before expansion rate of water absorption=(after water suction the front sample weight of sample weight-water suction)/water suction.
For under above-mentioned sample conditions of mixture ratios, obtain the stretching 7.21MPa of water uptake expansion material, elongation at break is 359%, and relative to the former state of not adding ionomer resin, elongation at break has 3 times significantly improve nearly.Water immersion test repeatedly; Sample is soaked 16h in normal temperature (23 ± 5) DEG C distilled water, after taking-up, at 70 DEG C, dries 8h, then be put in water and soak 16h, then dry 8h; After so repeatedly soaking, drying 4 loop cycles, survey its hardness, tensile strength and elongation, and press afore mentioned rules test volume expansion multiplying power.
After repeatedly soaking, under above-mentioned sample conditions of mixture ratios, obtain water uptake expansion material stretching 6.8MPa after this test, elongation at break is 267%, there is no obvious decline.
In water absorbing properties, the expansion rate of water absorption that with the addition of ionomer resin can reach 120%, and un-added sample is only 83%, and it is more than un-added sample nearly 40%, such result is only the resin about 5 mass parts for addition, is a more satisfactory result.This three components not only makes its mechanical property rise to some extent, also improves its water absorbent rate, also can illustrate that ionomer resin can play from the side and promote two-phase interface bonding force, improve interface adhesion, thus improve its mechanical property and water absorbing properties.Thisly ionomericly add the problem solving and add mechanical properties decrease after too much water-absorbing material component; And immersion test result shows that such uptake model has excellent Reusability performance repeatedly.
Prepared uptake model not only significantly improves water swelling rubber can not the shortcoming of secondary processing, and effectively improves its toughness and water absorbing properties, is a kind of water uptake expansion material of excellent combination property.
Embodiment 2
(1) before experiment, by 100 parts per weight of thermoplastic's elastomericss, 30 parts of sodium polyacrylate water-absorbing materials and 7 parts
w 501NC ionomer resin dries 4 hours under 90 DEG C of conditions.
(2) at room temperature, 100 parts per weight of thermoplastic's elastomericss are mixed 5 minutes with 0.5 part of weight part oxidation inhibitor in high-speed mixer, rotating speed is that 900rpm obtains just mixed thing.
(3) then at 180 DEG C, described pre-composition is added in Banbury mixer and carry out melting and plasticate 20 minutes, then add 7 parts of ionomer resin AMPLIFY IO 3701 and carry out melting and shear 10 minutes; Finally add sodium polyacrylate 30 weight part, mixing 15 minutes, obtain rubber unvulcanizate; Again added in single screw extrusion machine by product after mixing and carry out secondary plasticizing and cooling and dicing, temperature is 180 DEG C, and rotating speed is 60rpm, obtains high-performance thermoplastic uptake model.
(4) utilize injection moulding machine injection moulding for the batten of mechanical test, injection moulding machine each section of temperature is 195 ~ 215 DEG C.
According to Standard, following mechanical test is carried out for the injection moulding batten obtained:
The test of cross-linked rubber tensile stress-strain performance is carried out according to GB/T 528-1998.Test sample is dumbbell shape sample, sample overall length 75mm, presss from both sides pitch spacing from 45mm, gauge length 20mm, draw speed 500mm/min.Tear resistance test is carried out according to GB/T 528-2008.Draw speed 500mm/min.
All samples before testing, constant temperature 24 hours under 25 DEG C of constant temperatures.Probe temperature is 25 DEG C.
Water-swelling is tested: specimen size is 20 × 20 × 2mm, under room temperature condition, be soaked in after sample is weighed in deionized water, soak to take out after 96 hours and weigh, blot the moisture of specimen surface when weighing gently with thieving paper, the calculation formula of expansion rate of water absorption is as follows:
Sample weight × 100% before expansion rate of water absorption=(after water suction the front sample weight of sample weight-water suction)/water suction.
For under above-mentioned sample conditions of mixture ratios, obtain the stretching 7.41MPa of water uptake expansion material, elongation at break is 324%, and relative to the former state of not adding ionomer resin, elongation at break has 2.5 times significantly improve nearly.
Water immersion test repeatedly; Sample is soaked 16h in normal temperature (23 ± 5) DEG C distilled water, after taking-up, at 70 DEG C, dries 8h, then be put in water and soak 16h, then dry 8h; After so repeatedly soaking, drying 4 loop cycles, survey its hardness, tensile strength and elongation, and press afore mentioned rules test volume expansion multiplying power.
For under above-mentioned sample conditions of mixture ratios, obtain water uptake expansion material stretching 6.62MPa after this test, elongation at break is 358%, there is no obvious decline.
In addition, in water absorbing properties, the expansion rate of water absorption that with the addition of ionomer resin can reach 133%, and un-added component is only 83%, more than un-added sample nearly 50%, such result is only the resin about 7 mass parts for addition, is a more satisfactory result.This three components not only makes its mechanical property rise to some extent, also improves its water absorbent rate, also can illustrate that ionomer resin can play from the side and promote two-phase interface bonding force, improve interface adhesion, thus improve its mechanical property and water absorbing properties.Thisly ionomericly add the problem solving and add mechanical properties decrease after too much water-absorbing material component; And immersion test result shows that such uptake model has excellent Reusability performance repeatedly.
Embodiment 3
(1) before experiment, by 100 parts per weight of thermoplastic's elastomericss, 30 parts of sodium polyacrylate water-absorbing materials and 10 parts
w 501NC ionomer resin dries 4 hours under 90 DEG C of conditions.
(2) at room temperature, 100 parts per weight of thermoplastic's elastomericss are mixed 5 minutes with 0.5 part of weight antioxidant in high-speed mixer, rotating speed is that 1000rpm obtains just mixed thing.
(3) then at 195 DEG C, described pre-composition is added in Banbury mixer and carry out melting and plasticate 20 minutes, then add 10 parts of ionomer resin AClyn and carry out melting and shear 10 minutes; Finally add sodium polyacrylate 30 weight part, mixing 15 minutes, obtain rubber unvulcanizate; Again added in single screw extrusion machine by product after mixing and carry out secondary plasticizing and cooling and dicing, temperature is 190 DEG C, and rotating speed is 60rpm, prepares high-performance thermoplastic uptake model.
(4) utilize injection moulding machine injection moulding for the batten of mechanical test, injection moulding machine each section of temperature is 195 ~ 215 DEG C.
According to Standard, mechanical test is carried out for the injection moulding batten obtained.
The test of cross-linked rubber tensile stress-strain performance is carried out according to GB/T 528-1998.Test sample is dumbbell shape sample, sample overall length 75mm, presss from both sides pitch spacing from 45mm, gauge length 20mm, draw speed 500mm/min.Tear resistance test is carried out according to GB/T 528-2008.Draw speed 500mm/min.
All samples before testing, constant temperature 24 hours under 25 DEG C of constant temperatures.Probe temperature is 25 DEG C.
Water-swelling is tested: specimen size is 20 × 20 × 2mm, under room temperature condition, be soaked in after sample is weighed in deionized water, soak to take out after 96 hours and weigh, blot the moisture of specimen surface when weighing gently with thieving paper, the calculation formula of expansion rate of water absorption is as follows:
Sample weight × 100% before expansion rate of water absorption=(after water suction the front sample weight of sample weight-water suction)/water suction.
For under above-mentioned sample conditions of mixture ratios, obtain the stretching 6.87MPa of water uptake expansion material, elongation at break is 263%, and relative to the former state of not adding ionomer resin, elongation at break has 1.5 times significantly improve nearly.
Water immersion test repeatedly; Sample is soaked 16h in normal temperature (23 ± 5) DEG C distilled water, after taking-up, at 70 DEG C, dries 8h, then be put in water and soak 16h, then dry 8h; After so repeatedly soaking, drying 4 loop cycles, survey its hardness, tensile strength and elongation, and press afore mentioned rules test volume expansion multiplying power.
For under above-mentioned sample conditions of mixture ratios, obtain water uptake expansion material stretching 6.42MPa after this test, elongation at break is 297%, there is no obvious decline.
In addition, in water absorbing properties, the expansion rate of water absorption that with the addition of ionomer resin can reach 116%, and more than un-added sample nearly 30%, such result is only the resin about 10 mass parts for addition, is a more satisfactory result.This three components not only makes its mechanical property rise to some extent, also improves its water absorbent rate, also can illustrate that ionomer resin can play from the side and promote two-phase interface bonding force, improve interface adhesion, thus improve its mechanical property and water absorbing properties.Thisly ionomericly add the problem solving and add mechanical properties decrease after too much water-absorbing material component; And immersion test result shows that such uptake model has excellent Reusability performance repeatedly.
Claims (9)
1. a thermoplasticity uptake model, is characterized in that, described elastomerics comprises the component of following weight part:
2. elastomerics according to claim 1, it is characterized in that, described thermoplastic elastomer is selected from the combination of one or more in styrene-butadiene one styrene block copolymer, acrylonitrile-butadiene-styrene copolymer, thermoplastic polyurethane, polyolefin elastomer, ethylene-vinyl acetate copolymer, thermoplastic polyester elastomer.
3. elastomerics according to claim 1, is characterized in that, described water-absorbing material is selected from the combination of one or more in starch-series water-absorbing material, cellulose-based water-absorbing material and synthetic resins system water-absorbing material.
4. elastomerics according to claim 1, is characterized in that, described ionomer resin is Du Pont
the combination of one or more in W 501NC, Honeywell low molecule ionomer AClyn, Du Pont Surlyn, Tao Shi AMPLIFY IO 3701, Du Pont FORMION.
5. elastomerics according to claim 4, is characterized in that, the metal ion in described ionomer resin comprises Zn
2+, Na
+, K
+, Li
+.
6. elastomerics according to claim 1, is characterized in that, described oxidation inhibitor is selected from antioxidant 2246, antioxidant 1010, oxidation inhibitor 4426, antioxidant 1076, antioxidant 300.
7. the preparation method of the arbitrary described thermoplasticity uptake model of claim 1 to 6, is characterized in that, comprise following steps:
First, by the pre-mixing 1 ~ 10 minute in high-speed mixer of described thermoplastic elastomer and described oxidation inhibitor, pre-composition is obtained; After described pre-composition is added high-temperature mixer, at 160 ~ 230 DEG C, melting is plasticated 5 ~ 20 minutes, obtains melts;
Then, in described melts, add described ionomer resin, melting is sheared 1 ~ 5 minute, then adds described water-absorbing material melt blending 7 ~ 10 minutes, obtains mixing thing;
Finally, described mixing thing is carried out cooling and dicing after secondary plasticizing, the temperature of secondary plasticizing is 170 ~ 220 DEG C, and rotating speed is 60 ~ 120rpm, obtains described thermoplasticity uptake model.
8. the application of the arbitrary described thermoplasticity uptake model of claim 1 to 6, is characterized in that, for waterproofing and leakage-stopping and hermetic seal.
9. application according to claim 8, is characterized in that, for waterproofing and leakage-stopping engineering, subway, culvert, building construction, and water-sensitive sensor, biomaterial for medical purpose, soil improvement agent and water-holding agent field.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153102A (en) * | 2006-09-30 | 2008-04-02 | 易会安 | Water uptake expansion composition, water uptake expansion material and water uptake expansion packer |
| CN101983980A (en) * | 2010-10-29 | 2011-03-09 | 沈阳化工大学 | Method for improving performances of water-swelling rubber |
| CN103087367A (en) * | 2013-01-18 | 2013-05-08 | 中国石油天然气股份有限公司 | High-performance water swellable rubber and preparation method thereof |
| CN104136500A (en) * | 2012-01-04 | 2014-11-05 | 莫门蒂夫性能材料股份有限公司 | Polymer composites of silicone ionomers |
-
2015
- 2015-04-07 CN CN201510161293.6A patent/CN104693665A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153102A (en) * | 2006-09-30 | 2008-04-02 | 易会安 | Water uptake expansion composition, water uptake expansion material and water uptake expansion packer |
| CN101983980A (en) * | 2010-10-29 | 2011-03-09 | 沈阳化工大学 | Method for improving performances of water-swelling rubber |
| CN104136500A (en) * | 2012-01-04 | 2014-11-05 | 莫门蒂夫性能材料股份有限公司 | Polymer composites of silicone ionomers |
| CN103087367A (en) * | 2013-01-18 | 2013-05-08 | 中国石油天然气股份有限公司 | High-performance water swellable rubber and preparation method thereof |
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Application publication date: 20150610 |